Abstract
The article reviews the rich phenomena of metal-insulator transitions, anomalous metalicity, taking as examples iron and titanium oxides. The diverse phenomena include strong spin and orbital fluctuations, incoherence of charge dynamics, and phase transitions under control of key parameters such as band filling, bandwidth, and dimensionality. Another important phenomena presented in the article is a valence fluctuation which occur often in rare-earth compounds. We consider some Ce, Sm, Eu, Tm, and Yb compounds such as Ce, Sm and Tm monochalcogenides, Sm and Yb borides, mixed-valent and charge-ordered Sm, Eu and Yb pnictides and chalcogenides R4X3 and R3X4 (R = Sm, Eu, Yb; X = As, Sb, Bi), intermediate-valence YbInCu4 and heavy-fermion compounds YbMCu4 (M = Cu, Ag, Au, Pd). Issues addressed include the nature of the electronic ground states, the metal-insulator transition, the electronic and magnetic structures. The discussion includes key experiments, such as optical and magneto-optical spectroscopic measurements, x-ray photoemission and x-ray absorption, bremsstrahlung isochromat spectroscopy measurements as well as x-ray magnetic circular dichroism.
1. Introduction
Determination of the energy band structure of solids is a many-body problem. Band theory, a mean-field theory to treat this problem, in the framework of the local spin density approximation (LSDA), has been successful for many kinds of materials and has become the de facto tool of first-principles calculations in solid-state physics. It has contributed significantly to the understanding of material properties at the microscopic level. However, there are some systematic errors which have been observed when using the LSDA. In particular, the LSDA fails to describe the electronic structure and properties of the electron systems in which the interaction among the electrons is strong. These are now called strongly correlated electron systems, and many new concepts to address these phenomena have been constructed. However, the understanding of these systems is not complete. A wide variety of physical properties arise from the correlations among and electrons: metal-insulator transitions, valence fluctuations in the Kondo effect, heavy-fermion behavior, superconductivity, and so on.
The investigation of this class of systems goes back to the early 1960s. The main motivations at the time came from experiments on transition metal oxides, from the Mott metal-insulator transition, and from the problem of itinerant ferromagnetism. Theoretical progress in the field has been impeded however by the extreme difficulty of dealing with even the simplest model Hamiltonians appropriate for these systems, such as the Hubbard model and the Kondo lattice model [1]. Only in the one-dimensional case do we have a variety of theoretical tools at our disposal to study these models in a systematic manner. For two- and three-dimensional models, one is often unable to assess confidently whether a given physical phenomenon is indeed captured by the idealized Hamiltonian under consideration or whether a theoretical prediction reflects a true feature of this Hamiltonian, rather than an artifact of the approximation used in its solution. These difficulties originate in the nonperturbative nature of the problem and reflect the presence of several competing physical mechanisms for even the simplest models. The interplay of localization and lattice coherence, that of quantum and spatial fluctuations and that of various competing types of long-range order are important examples.
With the aim of undertaking a systematic investigation of the trends in some mixed-valent and charge- and orbital-ordering compounds, we present the theoretically calculated electronic structure, optical, magneto-optical, and photo-emission spectra for some and compounds. The main idea of the paper is to show how the modern band structure methods which take into account strong electron-electron interaction can properly describe the electronic structure and physical properties of strongly correlated electron systems.
In the first part of the article we concentrate on the description of the methods and the results for the transition metal oxides which possess different fascinating physical properties including charge and orbital ordering as well as metal-insulator transition (MIT). Metal-insulator transitions are accompanied by huge resistivity changes, even over tens of orders of magnitude, and are widely observed in condensed-matter systems [2]. Especially important are the transitions driven by correlation effects associated with the electron-electron interaction. The insulating phase caused by the correlation effects is categorized as the Mott Insulator. Near the transition point the metallic state shows fluctuations and orderings in the spin, charge, and orbital degrees of freedom. The properties of these metals are frequently quite different from those of ordinary metals, as measured by transport, optical, and magnetic probes. We consider the , , , and .
The second part of the paper is devoted to the strongly correlated systems such as CeFe2, Ce, Sm, and Tm monochalcogenides RX (R = Ce, Sm, Tm; X = S, Se, Te), Sm and Yb borides SmB6, YbB12, mixed-valent and charge-ordered Sm, Eu and Yb pnictides and chalcogenides and (R = Sm, Eu, Yb; X = As, Sb, Bi), intermediate-valence YbInCu4 and heavy-fermion compounds YbMCu4 (M = Cu, Ag, Au, Pd).
In rare-earth compounds, where levels are relatively close to the Fermi energy, various anomalous phenomena frequently appear. Most of them can be attributed to the hybridization between the states and conduction bands. A mixed-valence (MV) state is one of these phenomena. The MV phenomenon has attracted a great deal of interest during the last several decades in connection with valence fluctuations [3–7]. In the gas phase most rare earths are divalent, but in the solid state most are trivalent, due to the large cohesive energy gained by promoting a electron into an extended bonding state. The rare-earth compounds based on Sm, Eu, Tm, and Yb ions frequently exhibit a mixed-valence state consisting of divalent and trivalent valences. In the mixed-valence compounds, therefore, one must also consider the charge degrees of freedom of the ions in addition to the spin and orbital degrees of freedom.
It is necessary to distinguish between homogeneously mixed-valence compounds and inhomogeneously mixed-valence compounds. In the former, all the rare-earth ions occupy crystallographically equivalent sites, and, therefore, this is essentially a single ion property where the magnetic ion hybridizes with the sea of the conduction electrons, causing an exchange of the inner electron with the conduction band at the Fermi level. Such effects are expected to arise in systems where two electron configurations corresponding to occupation numbers and have nearly degenerate energies. So the ground state of a homogeneously mixed-valence compound is a quantum mechanical mixture of both the and the configuration on each rare-earth ion. Typical compounds exhibiting homogeneously mixed-valence phenomena are rare-earth materials TmSe, SmS (high-pressure golden phase), SmB6, YbB12, and YbInCu4.
In the case of inhomogeneously or static mixed-valence compounds, rare-earth ions with different valency occupy clearly different sites. However, at high temperatures they become homogeneously mixed-valence semimetals or valence-fluctuating insulators. Their electrons are strongly correlated and close to localization, that is, having a low effective kinetic energy. The electrons can hop between the magnetic ions with different valences due to thermal activation (a thermal valence-fluctuating state). If the intersite Coulomb repulsion is large enough, it may dominate the kinetic energy and, once the charge-disorder entropy due to hopping is low enough, lead to a charge-ordered transition at a critical temperature below which the valence fluctuation suppressed. The resulting inhomogeneously mixed-valence state consists of two species of ions with the and the configurations. This transition may be compared to a Wigner crystallization on a lattice [8], and its earliest example is the Verwey transition in magnetite [9], although this picture turned out to be too simplified for this compound [10, 11]. There are several charge-fluctuating inhomogeneous mixed-valence compounds containing rare-earth ions. They are the rare-earth pnictides , , and with the cubic anti- structure and rare earth chalcogenides (X = S, Se or Te) and with the structure.
2. Theoretical Framework
It is well known that the LSDA fails to describe the electronic structure and properties of the systems in which the interaction among the electrons is strong. In recent years more advanced methods of electronic structure determination such as LSDA plus self-interaction corrections (SIC-LSDA) [12], the LSDA+ [13] method, the GW approximation [14], and dynamical mean-field theory (DMFT) [1, 15, 16] have sought to remedy this problem and have met with considerable success. The LSDA+ method is the simplest among them and most frequently used in the literature therefore; we describe the method in detail.
2.1. LSDA+ Method
A rigorous formulation for the quasiparticle properties of solids is the Green function approach. The self-energy of the single-particle Green function is energy dependent and yields the correlation corrections to the single-particle (mean-field) approximation to the quasiparticle excitation spectrum described by . With a number of plausible assumptions, the LSDA+ approach has been related to the so-called GW approximation to in [17]. Already the simplest random phase approximation applied to for the Hubbard model yields a jump of at the Fermi level by the Hubbard . The more elaborate analysis of [17] results in a correlation correction to the mean-field approximation of the self-energy, which is downward below the Fermi level and upward above the Fermi level. As mean-field theory in a crystal describes always a delocalized situation and the LSDA Kohn-Sham potential is a well-proved approximation to the self-energy of weakly correlated situations [18], the suggestion is where is the projector onto a strongly correlated state.
The LSDA+ approach simply uses (1) to replace the LSDA Kohn-Sham potential in the self-consistency loop. This can be considered as a rough approximation to . Since the potential shift is taken to be constant in space, it does not deform the Kohn-Sham orbital . However, it shifts the levels of strongly correlated motion away from the Fermi level and thus removes incorrect hybridization with conduction states, which would spoil the calculated ground-state spin density. On the other hand, being also understood as an approximation to , it hopefully yields for the Kohn-Sham band structure the same quality of a working approximation to the quasiparticle excitation spectrum as it does in the case of weakly correlated metals.
The main idea of the LSDA+ is the same as in the Anderson impurity model [19]: the separate treatment of localized -electrons for which the Coulomb – interaction is taken into account by a Hubbard-type term in the Hamiltonian ( are orbital occupancies) and delocalized electrons for which the local density approximation for the Coulomb interaction is regarded as sufficient.
The spectrum of excitations for the shell of an electron system is a set of many-body levels describing processes of removing and adding electrons. In the simplified case, when every electron has roughly the same kinetic energy and Coulomb repulsion energy , the total energy of the shell with electrons is given by and the excitation spectrum is given by .
Let us consider ion as an open system with a fluctuating number of electrons. The correct formula for the Coulomb energy of – interactions as a function of the number of electrons given by the LDA should be [20]. If we subtract this expression from the LDA total energy functional and add a Hubbard-like term (neglecting for a while exchange and nonsphericity), we will have the following functional: The orbital energies are derivatives of (2): This simple formula gives the shift of the LDA orbital energy for occupied orbitals () and for unoccupied orbitals (). A similar formula is found for the orbital-dependent potential where variation is taken not on the total charge density but on the charge density of a particular th orbital : Expression (4) restores the discontinuous behavior of the one-electron potential of the exact density-functional theory.
The functional (2) neglects exchange and nonsphericity of the Coulomb interaction. In the most general rotationally invariant form the LDA+ functional is defined as [21, 22] where is the LSDA (or LDA as in [20]) functional of the total electron spin densities, is the electron-electron interaction energy of the localized electrons, and is the so-called “double counting” term which cancels approximately the part of an electron-electron energy which is already included in . The last two terms are functions of the occupation matrix defined using the local orbitals .
The matrix generally consists of both spin-diagonal and spin-nondiagonal terms. The latter can appear due to the spin-orbit interaction or a noncollinear magnetic order. Then, the second term in (5) can be written as [21–23] where are the matrix elements of the on-site Coulomb interaction which are given by with being screened Slater integrals for a given and The angular integrals of a product of three spherical harmonics can be expressed in terms of Clebsch-Gordan coefficients, and (8) becomes
The matrix elements and which enter those terms in the sum in (6) which contain a product of the diagonal elements of the occupation matrix can be identified as pair Coulomb and exchange integrals
The averaging of the matrices and over all possible pairs of , defines the averaged Coulomb and exchange integrals which enter the expression for . Using the properties of Clebsch-Gordan coefficients, one can show that where the primed sum is over . Equation (11) allows us to establish the following relation between the average exchange integral and Slater integrals: or explicitly
The meaning of has been carefully discussed by Herring [24]. In, for example, am electron system with electrons per atom, is defined as the energy cost for the reaction that is, the energy cost for moving an electron between two atoms where both initially had electrons. It should be emphasized that is a renormalized quantity which contains the effects of screening by fast and electrons. The number of these delocalized electrons on an atom with electrons decreases, whereas their number on an atom with electrons increases. The screening reduces the energy cost for the reaction given by (14). It is worth noting that because of the screening the value of in L(S)DA+ calculations is significantly smaller than the bare used in the Hubbard model [25, 26].
Some aspects of currently used LDA+ formulation and, in particular, of the determination of the parameters entering the model have been so far tied to the LMTO approach. The reformulation of the method for different basis sets has been made recently [27–29]. Pickett et al. [27] present a reformulation of the LDA+ method based on a local-orbital expansion (linear combination of atomic orbitals). The implementation of the LDA+ method by Bengone et al. [28] is based on the projector augmented wave (PAW) method [30], an efficient all-electron method without shape approximations on the potential or electron density. Based on a Car-Parrinello-like formalism [31], the PAW method allows complex relaxations and dynamical properties in strongly correlated systems. Cococcioni and De Gironcoli [29] reexamine the LDA+ method in the framework of a plane-wave pseudopotential approach (PWPP). A simplified rotational-invariant formulation was adopted. They demonstrate the accuracy of the method, computing structural, and electronic properties of a few systems including transition and rare-earth correlated metals, transition metal mono-oxides, and iron silicate [29], transition metal centers [32], and iron heme complexes [33].
In principle, the screened Coulomb and exchange integrals can be determined from supercell LSDA calculations using Slater’s transition-state technique [34] or from constrained LSDA calculations [27, 35, 36].
To obtain Hubbard and exchange parameter , Anisimov and coworkers [34, 36] propose to perform LMTO calculations in supercells in which the occupation of the localized orbitals of one atom is constrained. The localized orbitals of all atoms in the supercell are decoupled from the remainder of the basis set. This makes the treatment of the local orbitals an atomic-like problem making it easy to fix their occupation numbers and allows them to use Janak’s theorem [37] to identify the shift in the corresponding eigenvalue with the second-order derivative of the LDA total energy with respect to orbital occupation. It has, however, the effect of leaving a rather artificial system to perform the screening, in particular when it is not completely intra-atomic. In elemental metallic iron, for instance, only half of the screening charge is contained in the Wigner-Seitz cell [34]. This fact, in addition to a sizable error due to the atomic sphere approximation used, could be at the origin of the severe overestimation of the computed on-site Coulomb interaction. For example, Anisimov and Gunnarsson computed the effective on-site Coulomb interaction in metallic Fe and Ce. For Ce the calculated Coulomb interaction was found to be about 6 eV in good agreement with empirical and experimental estimates ranging from 5 to 7 eV [38], while the result for Fe (also about 6 eV) was surprisingly high since was expected to be in the range of 1-2 eV for elemental transition metals, with the exception of Ni [39, 40].
Cococcioni and De Gironcoli [29] provide an internally consistent, basis-set-independent, method based on a linear response approach for the calculation of the effective interaction parameters in the LDA+ method. They estimate the Hubbard in elemental iron at the experimental lattice parameter to be equal to eV in good agreement with the experimental data [39, 40].
Alternatively, the value of estimated from the photo-emission spectroscopy (PES) and X-ray Bremsstrahlung isochromat spectroscopy (BIS) experiments can be used. Because of the difficulties with unambiguous determination of , it can be considered as a parameter of the model. Then its value can be adjusted to achieve the best agreement of the results of LDA+ calculations with PES or optical spectra [28]. While the use of an adjustable parameter is generally considered an anathema among first principles practitioners, the LDA+ approach does offer a plausible and practical method to approximately treat strongly correlated orbitals in solids.
2.2. Magneto-Optical Effects
Magneto-optical (MO) effects refer to various changes in the polarization state of light upon interaction with materials possessing a net magnetic moment, including rotation of the plane of linearly polarized light (Faraday, Kerr rotation) and the complementary differential absorption of left and right circularly polarized light (circular dichroism). In the near visible spectral range these effects result from excitation of electrons in the conduction band. Near X-ray absorption edges, or resonances, magneto-optical effects can be enhanced by transitions from well-defined atomic core levels to transition symmetry selected valence states.
For a crystal of cubic symmetry, where the magnetization is parallel to the -axis, the dielectric tensor is composed of the diagonal and and the off-diagonal components in the form A complete description of the MO effects is given by the four nonzero elements of the dielectric tensor or, equivalently, by the complex refractive index for several normal modes corresponding to the propagation of pure polarization states along specific directions in the sample, which can be obtained by solving Maxwell’s equations [41]. Two of these modes are for circular components of opposite (±) helicity with the wave vector and have indices
The other two modes are for linear polarizations with [42]. One has the electric vector and index . The other has and .
At normal light incidence the relation between the polar complex Kerr angle and the dielectric tensor components is given by the expression [43]
X-ray magnetic circular dichroism is given by and is first-order in . Magnetic linear dichroism (also known as the Voigt effect) is quadratic in . The Voigt effect is present in both ferromagnets and antiferromagnets, while the first order MO effects in the forward scattering beam are absent with the net magnetization in antiferromagnets.
Within the one-particle approximation, the absorption coefficient for incident X-ray of polarization and photon energy can be determined as the probability of electronic transitions from initial core states with the total angular momentum to final unoccupied Bloch states where and are the wave function and the energy of a core state with the projection of the total angular momentum ; and are the wave function and the energy of a valence state in the th band with the wave vector ; is the Fermi energy.
is the electron-photon interaction operator in the dipole approximation where are the Dirac matrices, is the polarization unit vector of the photon vector potential, with , . Here, and denote, respectively, left and right circular photon polarizations with respect to the magnetization direction in the solid. Then, X-ray magnetic circular and linear dichroisms are given by and , respectively.
The Kerr effect has now been known for more than a century, but it was only in recent times that it became the subject of intensive investigations. The reason for this recent development is twofold: first, the Kerr effect gained considerable interest due to modern data storage technology, because it can be used to “read” suitably stored magnetic information in an optical manner [44], and, second, the Kerr effect has rapidly developed into an appealing spectroscopic tool in materials research. The technological research on the Kerr effect was initially motivated by the search for good magneto-optical materials that could be used as information storage medium. In the sequence of this research, the Kerr spectra of many ferromagnetic materials were investigated. An overview of the experimental data collected on the Kerr effect can be found in the review articles by Buschow [45], Reim and Schoenes [46], and Schoenes [43].
The quantum mechanical understanding of the Kerr effect began as early as 1932 when Hulme [47] proposed that the Kerr effect could be attributed to spin-orbit (SO) coupling (see also Kittel [48]). The symmetry between left- and right-hand circularly polarized light is broken due to the SO coupling in a magnetic solid. This leads to different refractive indices for the two kinds of circularly polarized light, so that incident linearly polarized light is reflected with elliptical polarization, and the major elliptical axis is rotated by the so-called Kerr angle from the original axis of linear polarization. The first systematic study of the frequency-dependent Kerr and Faraday effects was developed by Argyres [49] and later Cooper presented a more general theory using some simplifying assumptions [50]. The very powerful linear response techniques of Kubo [51] gave general formulas for the conductivity tensor which are being widely used now. A general theory of frequency dependent conductivity of ferromagnetic (FM) metals over a wide range of frequencies and temperatures was developed in 1968 by Kondorsky and Vediaev [52].
The main problem afterward was the evaluation of the complicated formulas involving MO matrix elements using electronic states of the real FM system. With the tremendous increases in computational power and the concomitant progress in electronic structure methods, the calculation of such matrix elements became possible, if not routine. Subsequently much earlier, simplified calculations have been shown to be inadequate, and only calculations from “first principles” have provided, on the whole, a satisfactory description of the experimental results [53]. The existing difficulties stem either from problems using the local spin density approximation (LDA) to describe the electronic structure of FM materials containing highly correlated electrons or simply from the difficulty of dealing with very complex crystal structures. For 15 years after the work of Wang and Callaway [53] there was a lull in MO calculations until MO effects were found to be important for magnetic recording and the computational resources had advanced. Different reliable numerical schemes for the calculation of optical matrix elements and the integration over the Brillouin zone have been implemented, giving essentially identical results [54]. Prototype studies have been performed using modern methods of band theory for Fe, Co, and Ni [55–59]. Following the calculations for the elemental ferromagnets, a number of groups have evaluated the MO and XMCD spectra for more interesting compounds [10, 60–88] and multilayers [89–102].
3. Iron Oxides
3.1. Cubic
The problem of a theoretical description of metal-insulator transitions has a challenging history of almost 70 years. It was first addressed by Verwey, de Boer, and Peierls in the late 1930s; they pointed out the extremely important role of electron-electron correlations in a partially filled electron band in transition metal oxides [103, 104], for example, nickel oxide (NiO) and magnetite (). In both systems the metal-insulator transition occurs, violating the Bloch-Wilson band-insulator concept, the only one known at that time [105–108]. These earlier observations launched the long and continuing history of the field of strongly correlated electrons. In the past 80 years, much progress has been achieved from both theoretical and experimental sides in understanding strongly correlated electrons and metal-insulator transitions [2]. However, the charge ordering proposed by Verwey behind the metal-insulator transition [9, 109, 110] in remains at the focus of active debate [111, 112].
Historically, magnetite, discovered before 1500 B.C., is the first known magnet and is extensively used for industrial applications, notably in magnetic recording. Most of the properties of magnetite have been thoroughly studied and are well documented [113, 114]. However, the electronic structure of as well as that of many other MIT compounds is still a subject of debate [115–119].
is a strongly correlated compound which is ferrimagnetically ordered below a high transition temperature (~850 K). The valence of various atoms is described by the formal chemical formula, . The tetrahedral lattice sites ( sites) in the inverse spinel structure are occupied by ions, whereas the octahedral lattice sites ( sites) are occupied alternately by equal numbers of and . At K undergoes a first-order phase transition (Verwey transition) [9]. This is a particular MIT that has been studied for quite some time [120]. The Verwey transition is characterized by an abrupt increase in the electrical conductivity by two orders of magnitude on heating through [121–123]. Verwey and co-workers [9, 110] were the first to point out that this transition is associated with an electron localization-delocalization transition. The ion can be regarded as an “extra” electron plus an ion. When all sites are equivalent, the “extra” electron is moving between ions and the system is a mixed-valent metal, with average FeB-valence, . The Verwey phase transition below is accompanied by long-range charge ordering (LRCO) of and ions on and sites of the sublattice. Indeed, studies by electron and neutron diffraction and nuclear magnetic resonance [124–126] show that below the and sites are structurally distinguishable with the crystal structure slightly distorted because of the charge ordering. Just how these charges arrange themselves has been the subject of debate [120] since Verwey first proposed that, below , all and sit on different chains [9].
The electronic structure of has been investigated experimentally by means of soft X-ray spectroscopy [127–129], Seebeck-effect measurements [130, 131], photoelectron spectroscopy [132–139], optical [140, 141] and MO spectroscopies [142–149], and magnetic dichroism [150, 151]. The optical data [141] indicate a gap of 0.14 eV between occupied and empty electronic states and also show a strong temperature dependence of the optical conductivity in the energy region of 0 to 1 eV.
The interpretation of the optical and MO spectra of is very difficult due to the existence of three kinds of iron atoms, that is, , , and . The substitution for one of the types of iron ions by nonmagnetic ions provides a possibility for distinguishing transitions from various sites. There are several such experimental studies in the literature. Simsa and coworkers reported the polar Kerr rotation and ellipticity of as well as the influence of a systematic substitution of by in the 0.5–3.0 eV energy range [144, 145]. Zhang and coworkers reported the polar Kerr spectra and the off-diagonal element of the dielectric tensor of between 0.5 and 4.3 eV. They also reported spectra of and between 0.5 and 5.0 eV [142]. Finally, recent investigation of the optical and MO spectra of and and substitution has been carried out in [143].
Energy band structure calculations for in the high-temperature cubic phase have been presented in [152] using the self-consistent spin-polarized augmented plane wave method with the local spin-density approximation. The calculations show that is a half-metallic ferrimagnet. The Fermi level crosses only the minority-spin energy bands consisting of orbitals on the Fe() sublattice. There is an energy gap for the majority-spin bands at the Fermi level. A similar energy band structure of was obtained in [153] using the LMTO method. The energy band structure for charge ordering in the low-temperature phase of has been calculated in [10, 11, 154, 155] using the LMTO method in the LSDA+ approximation.
3.1.1. Crystal Structure and Charge Ordering
crystallizes in the face-centered cubic (FCC) inverse spinel structure (Figure 1) with two formula units (14 atoms) per primitive cell. The space group is (no. 227). The oxygen atoms form a close-packed face-centered cubic structure with the iron atoms occupying the interstitial positions. There are two types of interstitial sites both occupied by the iron atoms. One site is called the or site, tetrahedrally coordinated by four ions composing a diamond lattice. The interstices of these coordination tetrahedra are too small for larger ions, and this site is occupied only by ions. Another cation site is called the or site, and is coordinated by six ions forming slightly distorted octahedra, which line up along the axes of the cubic lattice sharing edges. The point symmetry of the site is . This site forms exactly one-half of a face-centered cubic lattice. The lattice of the site can be considered as a diamond lattice of cation tetrahedra, sharing corners with each other. All the tetrahedra on the same (e.g., ) plane are isolated. In the following, we refer to axes or chains and axes or chains. The direction is , is and the -axis is . All the Fe octahedral or sites lie on either or chains. It should be mentioned also that the distances FeA-O1 and FeB-O2 are different and equal to 1.876 and 2.066 Å, respectively.
Details concerning the mechanism of the Verwey transition and the type of LRCO are still unclear. Many elaborate theories for the Verwey transition have been proposed. Anderson [156] pointed out the essential role of short-range charge ordering (SRCO) in the thermodynamics of the transition. The observed entropy change in the transition [(~0.3 to 0.35)-site mole] is decisively smaller than the expected in a complete order-disorder transition. Anderson interpreted the Verwey transition as a loss of the LRCO of the “extra” electrons on the sublattice at temperatures above , while the short-range charge order is maintained across the transition. Using a Hartree-Fock analysis, Alben and Cullen and Callen [157–159] showed that an ordering transition could occur in as a function of the ratio , where is the bandwidth of the “extra” electrons in the absence of disorder. The transition in this case is of second order, while experimentally a first-order transition is observed. The conduction mechanisms in have been reviewed by Mott [160–162] (see also [120, 163]). A basic problem concerning magnetite is that both the localization of the valence states and the mixing of the oxygen states and iron states are considerable.
In the disordered high-temperature phase the sites are occupied by equal numbers of and ions randomly distributed between and sites. Below the system undergoes a first-order transition accompanied by long-range charge ordering of and ions on the sites. Verwey from the very beginning proposed a rather simple charge separation: chains occupied only by ions and chains by ions (or vice versa) [9]. Since that time the type of charge ordering has been the subject of debate [120]. As an example, in Mizoguchi’s model [164, 165] ions run in pairs of followed by along each chain. Another charge ordering considers three alternating with one on one half of the chains, and a sequence of three alternating with one on the other half and so on [120]. Despite the wealth of effort devoted to investigating the low-temperature phase of magnetite, there is still no completely satisfactory description of the ordering of the Fe atoms on the octahedral or sites in this spinel structure. In addition some experimental measurements disproved the orthorhombic Verwey CO model. These experiments have clearly established the rhombohedral distortions of the cubic unit cell first detected by Rooksby et al. from X-ray powder diffraction [166, 167]. Furthermore, observations of superstructure reflections revealed half-integer satellite reflections, indexed as on the cubic unit cell, which points to a doubling of the unit cell along the -axis and shows the symmetry to be monoclinic [168, 169]. The observation of monoclinic lattice symmetry was also confirmed by a single-crystal X-ray study [170], whereas the observation of a magnetoelectric effect indicated even lower symmetry in the low-temperature phase [171]. Although clear evidence of the monoclinic lattice symmetry below was obtained, small atomic displacements have not been fully resolved so far. The absence of a definitive, experimentally determined structure gives rise to many theoretical models proposed for the low-temperature (LT) phase of magnetite [172]. In particular, purely electronic [158, 159, 164, 173] and electron-phonon [174–176] models for CO, as well as a bond-dimerized ground state without charge separation [177], have been proposed.
Recent bond-valence-sum analysis [178] of high-resolution neutron and X-ray powder diffraction data results in a small charge disproportion of only 0.2 between cations with the 2+ and 3+ formal valency [111, 179]. This interpretation has been the subject of much controversy [112, 180]. However, the smallness of the charge-order parameter was reproduced in an electronic structure study of the refined low-temperature crystal structure using the local-spin-density approximation (LSDA)+ method [181, 182]. In particular, a more complicated charge-ordering pattern inconsistent with the Verwey CO model was obtained. In addition to that, the occupancy self-consistently obtained in the LSDA+ calculations is strongly modulated between the and cations, yielding a distinct orbital order with an order parameter that reaches 70% of the ideal value [181]. Since no direct experimental confirmation of this charge- and orbital-order pattern is so far available, the interpretation of these results is still open to debate. However, this behavior seems to be universal and has recently been found in several other charge-ordered mixed-valent systems [182–186].
In order to check the pertinence of the CO model obtained self-consistently in [181], authors of [187] carried out a detailed theoretical study of exchange coupling constants, optical conductivity, magneto-optical (MO) Kerr effect, and X-ray absorption at the O edge of low-temperature and compared the results of the calculations to the available experimental data.
3.1.2. LSDA Band Structure
Figure 2 shows the partial density of states of obtained from the LSDA calculation. The occupied part of the valence band can be subdivided into several regions separated by energy gaps. The oxygen bands, which are not shown in the figure, appear between −20.0 and −19.7 eV for both spins with the exchange splitting of about 0.2 eV. The next group of bands in the energy region −7.4 to −3.4 eV is formed mostly by oxygen states. The Fe energy bands are located above and below at about −4.0 to 3.0 eV. As indicated from Figure 2, the exchange splitting between the spin-up and spin-down electrons on the Fe atom is about 3.5 eV. In addition to the exchange splitting, the five levels of the Fe atom are split due to the crystal field. At the site ( point symmetry) in the spinel structure the crystal field causes the orbitals to split into a doublet ( and ) and a triplet (, , and ). The octahedral component of the crystal field at the site is strong enough that the (, , and ) and ( and ) orbitals form two separate nonoverlapping bands. At the site the crystal field is trigonal (), as a result the orbitals split into a singlet and a doublet . However, the splitting of the band is negligible in comparison with its width in LSDA calculations; therefore, in the following we will denote the states formed by and orbitals as states. Accordingly, we present in Figure 2 the DOS of “” orbitals as a sum of the and ones. The crystal-field splitting is approximately 2 eV for the atom and 1 eV for the atom. This difference may be attributed to the large covalent mixing of the orbitals with its six nearest neighbors of the same kind. The spin-polarized calculations show that in the high-temperature phase is a half-metallic ferrimagnet. The Fermi level crosses only the majority spin energy bands, consisting of spin-up orbitals on the sublattice (Figure 2). There is an energy gap for the minority spin bands at the Fermi level. Spin-orbit splitting of the energy band at Γ is about 0.02 eV and much smaller than the crystal-field splitting.
In the magnetic moments within the and the sublattices are ferromagnetically aligned while the two sublattices are antiferromagnetic with respect to each other. This magnetic structure was first proposed by Neel [188] to explain the magnetization data and was later confirmed by neutron scattering measurements [189]. Measurements indicated that the magnetic moment of an iron atom on the site is much smaller than the 5.0 of a pure ion [190]. This is an indication of strong hybridization between the orbitals of . The orbital magnetic moment is rather small for all the atoms due to small spin-orbit coupling.
3.1.3. LSDA+ Band Structure
The application of LSDA calculations to is problematic, because of the correlated nature of electrons in this compound. The intersite Coulomb correlation is well described by the LSDA. However, the on-site Coulomb interaction, which is a driving force for Mott-Hubbard localization, is not well treated within LSDA. As a result, LSDA gives only a metallic solution without charge ordering. The LSDA+ calculations [10] started from a configuration for ions on the tetrahedral site of the sublattice and and for and ions on octahedral site of the sublattices and , respectively. was applied to all the states, and the occupation numbers were obtained as a result of the self-consistent relaxation.
Figures 3 and 4 show the energy band structure along the symmetry lines and the total and partial density of states obtained from the LSDA+ calculation. In contrast to LSDA, where the stable solution is a metal with a uniform distribution of the electrons on the octahedral sites, the LSDA+ gives a charge-ordered insulator with a direct energy gap value of 0.19 eV at the Γ point. The experimental optical measurements [141] gave a gap of 0.14 eV at K. The energy gap occurs between the (the top of valence band) and (bottom of empty conduction band) states (Figure 4). Actually, the LSDA+ band structure calculations support the key assumption that Cullen and Callen have made earlier [157–159] in proposing the one-band model Hamiltonian, where it was assumed that the “extra” electron moves in the band split off below the rest of the bands of other symmetries. Two electrons at the orbitals situated in the close vicinity of the Fermi level are mostly localized. Other electrons at the site are well hybridized with oxygen -electrons (Figure 4). The screening of the Coulomb interaction in is very effective and the system is close to the metallic state. Even a small change in the ratio (which can be modeled by changing of the occupation numbers of the orbital at the and sites in the framework of the “virtual crystal approximation”) leads to the closing of the energy gap and a suppression of the metal-insulating transition [10].
(a)
(b)
3.1.4. Optical and MO Properties
After the consideration of the above band structure properties, we turn to the optical and MO spectra. In Figure 5 experimental optical reflectivity and the diagonal part of the dielectric function of are compared to the theoretical ones calculated within the LSDA and LSDA+ approaches. Better agreement between the theory and the experiment was found when the LSDA+ approximation was used. As was mentioned above, the LSDA theory produces the metallic solution and, therefore, gives a wrong asymptotic behavior for the optical reflectivity and the dispersive part of the dielectric function as . In Figure 6 we show the calculated and experimental absorptive part of the diagonal optical conductivity spectra in a wide energy range. The characteristic features of the LSDA calculation of is an erroneous peak at 1.9 eV which is absent in the experimental measurement. The absence of this peak in the experiment indicates that the LSDA calculations produce incorrect energy band positions. Accounting for the Coulomb repulsion strongly influences not only the electronic structure but also the calculated optical spectra of . The LSDA+ calculations make better job in describing the optical spectra of than the LSDA approach (see Figures 5 and 6). The calculated optical conductivity spectrum (Figure 6) can be sorted into the following groups of interband transitions: (1) the interband transitions between the Fe bands below 2.5 eV, (2) the transitions from O to Fe bands in the region of 2.5 to 9 eV, and (3) Fe and O interband transitions above 9 eV. To avoid misunderstanding, we should mention that here and in the following when talking about transitions we mean that the energy bands involved in the transitions have predominantly character; however, the contribution of or states to these bands is sufficient to provide a significant transition probability through optical dipole matrix elements.
Let us consider now the magneto-optical properties of . In Figure 7 we show the experimentally measured [146] Kerr rotation and Kerr ellipticity MO spectra of , as well as the off-diagonal parts of the dielectric function calculated with the LSDA and LSDA+ approximations [10]. This picture clearly demonstrates that the better description is achieved with the LSDA+ approach.
One should mention that, although the O → Fe interband transitions, which start already from about 2.5 eV, play an important role in the formation of the optical spectra of , the Kerr spectra are mostly determined by transitions between energy bands which have predominantly Fe character. The reason for this is that the spin-orbit and exchange splitting of O states is much smaller in comparison with the Fe ones. The minimum in the Kerr rotation spectrum at 0.9 eV is due to the () interband transitions. The second maximum at about 2 eV is associated with the interband transitions. The minimum in the Kerr rotation spectrum between 3 and 4 eV can be associated with the transitions.
All the experimental measurements of the Kerr spectra of [142–147] have been performed at room temperature. The LSDA+ calculations, in comparison with the LSDA ones, describe better the electronic structure, optical and MO properties not only in the low-temperature semiconducting phase but also in the high-temperature metallic phase of . This leads to a conclusion that Fe electrons remain “correlated” above . The main effect of heating through is a disappearance of the long-range charge order on the sublattice. This leads to the rearrangement of the electronic states in a small vicinity of the Fermi level and to the closing of the energy gap. However, high-energy Hubbard bands, whose energy position is mainly determined by on-site exchange and correlation interactions, remain almost unaffected ( to 5 eV is much larger than eV). This picture is supported by recent optical measurements [141], which show a strong temperature dependence of the optical properties of only in the range from 0 to 1 eV. The absolute value of the measured prominent peak in the optical absorption for photon energies around 0.6 eV determined by the interband transitions gradually decreases by about 30% when changing the temperature from 10 K to 490 K. However, the other parts of the spectrum change very little.
Finally, we would like to point out that, while the LSDA+ approach does a better job than the LSDA in the treatment of correlation effects, it is still unclear how well it performs in evaluating the subtle energies and interactions affecting the charge-ordered ground state and the higher-temperature short-range ordered states.
3.1.5. X-Ray Magnetic Circular Dichroism
The XMCD technique developed in recent years has evolved into a powerful magnetometry tool to separate orbital and spin contributions to element-specific magnetic moments. XMCD experiments measure the absorption of X-rays with opposite (left and right) states of circular polarization. The XMCD spectra in core level absorption are element specific and site selective, thus providing valuable information on the energy position of empty states in a wide energy interval.
The interpretation of the experimental XMCD spectra of [150, 151] is very difficult due to the existence of three kinds of iron atoms, that is, , , and . The substitution for one of the types of iron ions by another transition metal ion provides a possibility for distinguishing transitions from various sites. There are several such experimental studies in the literature. Koide and coworkers reported the XMCD spectra at the and Co M2,3 core-absorption edges in and [151]. For the M2,3 prethreshold MCD spectra were measured above and below the Verwey transition temperature. Van Der Laan et al. [192] reported the XMCD spectra at the Ni edges of (trevorite). The Ni edge magnetic circular dichroism measurements of ferrimagnetic (, 0.26, 0.50, and 0.75) were reported by Pong et al. [193]. Magnetic circular dichroism is reported for ferrite in [194] with the measurements performed on the and core levels of Mn and Fe. The electronic structure, spin and orbital magnetic moments, and XMCD spectra of the series , , , and are presented in [191]. The XAS and XMCD spectra at , and edges for transition metals sites were calculated.
In Figure 8 the experimentally measured Fe XMCD spectra [150] in are compared to the theoretical ones calculated within the LSDA+ approach [191]. The dichroism at the and edges is influenced by the spin-orbit coupling of the initial core states. This gives rise to a very pronounced dichroism in comparison with the dichroism at the edge. Two prominent negative minima of Fe XMCD spectrum are derived from iron ions at octahedral sites. The major positive maximum is from ions. In the LSDA+ calculations of the charge-ordered , the XMCD spectra have slightly different shape for the and ions. The LSDA+ calculations are not able to produce the small positive shoulder at the high-energy side of the main peaks of the Fe XMCD spectrum.
The XMCD spectra at the edges are mostly determined by the strength of the SO coupling of the initial core states and spin-polarization of the final empty states, while the exchange splitting of the core states as well as the SO coupling of the valence states are of minor importance for the XMCD at the edge of transition metals [195].
To investigate the influence of the initial state on the resulting XMCD spectra, the XAS and XMCD spectra of at the edge were also calculated. The spin-orbit splitting of the core level is about one order of magnitude smaller than for the level in . As a result the magnetic dichroism at the edge is smaller than at the edge. In addition the and spectra are strongly overlapped, and the spectrum contributes to some extent to the structure of the total spectrum in the region of the edge. To decompose a corresponding experimental spectrum into its and parts will therefore be quite difficult in general.
In Figure 9 the experimentally measured Fe XMCD spectrum [151] in is compared to the theoretical one calculated within the LSDA+ approach [191]. In the magnetic moments within the and the sublattices are ferromagnetically aligned while the two sublattices are antiferromagnetic with respect to each other. The XMCD spectra are positive at the and negative at the edge at the tetrahedral sites and vice versa for the octahedral ones. The interpretation of the experimental Fe XMCD spectrum is very difficult without a knowledge of the band structure and corresponding transition matrix elements because this spectrum is a superposition of six spectra (from , , and sites) appearing simultaneously in a rather small energy range.
3.2. Low-Temperature Monoclinic
3.2.1. Crystal Structure
The low-temperature structure was shown to have a supercell with space group from X-ray and neutron diffraction [111, 179]. However, recent structural refinement (at 90 K) was only possible in the centric monoclinic space group with of the cubic spinel subcell and eight formula units in the primitive unit cell [111, 179]. Since the refinement for the space group was found to be unstable, additional orthorhombic symmetry constraints were also applied. This is equivalent to averaging the true superstructure over the additional symmetry operators; that is, each site in the unit cell is averaged over four nonequivalent subsites in the large supercell. Note, however, that such an approximation is robust in the sense of smallness of any distortions from the subcell to the monoclinic cell (according to [179] these are of ~0.01 Å). Previous structure refinement below obtained by Iizumi et al. resulted in a subcell of the unit cell and imposed orthorhombic symmetry constraints on the atomic positions [196]. In particular, a refinement based on an approximation of the true crystal structure by a centric space group or polar was proposed. But a charge-ordered arrangement has not been identified in this refinement, although large atomic displacements of Fe and O atoms were found. This is in strong qualitative contrast to the recent structure refinement proposed by Wright et al. where clear evidence of CO below the transition has been found [111, 179].
According to the refinement the octahedral sites are split into two groups with different values of the averaged Fe–O bond distances, with and sites being significantly smaller than and (– are crystallographically independent sites according to the notation in [111, 179]). A different averaged Fe–O bond distance is a sensitive experimental indicator of the cation charge state. Quantitative analysis of the valence state of both groups using the bond-valence-sum (BVS) method shows that the octahedral sites fall into two clear groups with respect to the estimated value of valence. The result is a charge disproportion of 0.2 between large ( and ) and small ( and ) sites (which has been referred as the class I CO model). Another possible class of CO arises from the symmetry-averaging orthorhombic constraint. There are 32 charge-ordered models which are referred to as class II CO because large ( and ) and small ( and ) sites could be averaged over () and () subsites, respectively. The symmetry averaging results in decrease of the more pronounced charge separation of in the full superstructure (class II CO) down to in the subcell. The Anderson criterion is not satisfied by any of the class I or class II CO models. This is remarkable because the Anderson criterion has been widely used in many CO models [164, 173]. However, class II, as was shown from electrostatic repulsion energy estimations, appears to be more plausible than the class I arrangement.
Recently this interpretation of the refined crystal structure has been found to be controversial. The lack of atomic long-range CO and, as a result, an intermediate valence regime below the Verwey transition were proposed [112, 180]. It is argued that the difference of the average Fe–O distances between compressed and expanded FeO6 octahedra, which could be considered as a maximum limit of charge disproportionation, has the same order as the total sensitivity (including experimental errors) of the bond-valence-sum method. This remarkable controversy shows that the understanding of the system is far from satisfactory.
3.2.2. Band Structure
In order to account for the strong electronic correlations in the Fe shell, at least on the static Hartree-Fock level, the authors of [155] calculated the electronic structure of the LT phase of using the LSDA+ method. The value of the parameter for Fe cations estimated using different experimental and theoretical technics lies in the range of 4.5–6 eV [154, 173, 197]. A reasonably good agreement of the calculated gap value of 0.18 eV with the experimental value [141] of 0.14 eV at 10 K was obtained using the value of 5 eV. Note, however, that the charge and orbital order derived from the LSDA+ calculations does not depend on the exact value when it is varied within the above-mentioned limits. The value of the Hund’s coupling eV was estimated from constrained LSDA calculations [27]. In the following all results presented in the paper were obtained using a value of 5 eV.
Figure 10 shows the LSDA+ band structure and the total DOS [155] calculated self-consistently for the low-temperature structure of using the Coulomb interaction parameter eV and exchange coupling eV. The corresponding partial DOSs are shown in Figure 11. The LSDA+ calculations give results qualitatively distinct from those of the LSDA. An indirect energy gap of 0.18 eV opens in the minority spin channel between M and Γ symmetry points. One of the minority spin states of and ions becomes occupied while the and states are pushed above the chemical potential. Although, as will be discussed below, the calculated disproportion of charges is significantly less than 1, in the following we use the notations and for and cations, respectively, having in mind the difference of their occupations. The top of the valence band is formed by the occupied states of and cations. The bottom of the conduction band is formed predominantly by the empty states of and cations. The remaining unoccupied states of and cations are pushed by the strong Coulomb repulsion to energies above 2.5 eV. Majority-spin states are shifted below O states, which form a wide band in the energy interval between −7 and −2 eV. This is in strong contrast with the uniform half-metallic solution obtained by the LSDA.
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Bands corresponding to the cations are fully occupied (empty) for minority- (majority-) spin states, respectively, and already in the LSDA do not participate in the formation of bands near the Fermi level. The LSDA+ method does not strongly affect these bands, which lie in the energy interval of −6 eV below and 1-2 eV above the Fermi level.
3.2.3. Charge Ordering
The obtained solution for CO of and cations on the sublattice is described by a dominant charge (and spin) density wave, which originates from alternating chains of ions on octahedral sites and ions on sites (see Table 1 and Figure 2 in [181]). A secondary modulation in the phase of CO, which is formed by the chain of alternately “occupied” ions on the sites and “empty” ions on sites, was found. This is consistent with a [001] nesting vector instability at the Fermi surface in the minority electron states which has been recently revealed by the LSDA calculations for the cubic phase [198]. The calculated CO scheme coincides with the class I CO model proposed by Wright et al. [111, 179]. All the tetrahedra formed by cations have either a 3 : 1 or 1 : 3 ratio of and ions. Thus, the LSDA+ calculations confirm that the Anderson criterion is not satisfied in the LT phase. However, it should be pointed out that the Anderson criterion was introduced under the assumption of equal interatomic distances within each tetrahedron, whereas in the distorted LT structure the iron-iron distances vary from 2.86 to 3.05 Å. The same CO pattern has been recently confirmed by other LSDA+ calculations [182].
An analysis of the minority occupation matrices of cations confirms very effective charge disproportion within the minority-spin subshell. In particular, one of the states of and cations is almost completely filled with the occupation . On the other hand, the other two orbitals of the cations have significantly smaller population of about 0.04. The occupation numbers of orbitals for and cations do not exceed 0.1–0.17, which gives a value of about 0.7 for the largest difference of the populations of and states. The occupation numbers of the minority-spin orbitals and the net occupations of the and states are given in the last two columns of Table 1.
The change of the occupations caused by the charge ordering is very effectively screened by the rearrangement of the other Fe electrons. A significant contribution to the screening charge is provided by states. Although the bands originating from these states are located well above the energy gap, the minority spin orbitals form relatively strong bonds with states of the oxygen octahedron and, as a result, give an appreciable contribution to the occupied part of the valence band. The energy of states is lower than the energy of corresponding states, and the former give a significantly larger contribution to the part of the valence band formed mainly by O states. Because of the stronger covalency of the –O bonds, the net occupation of states becomes larger (see the last column of Table 1). The resulting charge difference (0.23) and disproportionation of the total electron charges inside the atomic spheres of and ions (0.24) are in reasonably good agreement with the value of 0.2 estimated from a BVS analysis of the structure [111, 179]. The above-mentioned screening of the changes in the minority occupations reduces the energy loss due to the development of charge order incompatible with the Anderson criterion in the LT phase of .
Hence, due to the strong screening effects, the order parameter defined as the difference of the net charges of cations does not provide conclusive evidence for CO. This explains why the BVS analysis does not give a convincing proof of CO existence. Apparently, a well-defined order parameter is the difference of the occupations of the minority-spin states for and cations which amounts to 70% of the ideal ionic CO model and clearly indicates the existence of a charge-ordered ground state below the Verwey transition.
The LSDA+ calculations were also performed for the assumption of Verwey charge order in the structure [155]. However, instead of the assumed Verwey CO, the same self-consistent solution as the one described above was found. Therefore, the Verwey CO model is unstable in the distorted structure. It is well known that with increasing value localization is effectively increased. Remarkably, even for a value increased up to 7-8 eV no Verwey-like CO pattern was found self-consistently in the distorted structure. On the contrary, the LSDA+ calculations performed for an undistorted supercell of the structure result in an insulating CO solution which is compatible with the Verwey CO model. Altogether this implies that the Verwey CO model is unstable under a structure distortion from the high-symmetry cubic into the low-symmetry phase.
Also authors performed LSDA+ calculations [155] with the same and parameters (5 and 1 eV, resp.) for the assumption of one of the 32 class II CO models within supercell of , which is shown in Figure 2 in [179]. But it was found that this kind of CO is unstable and the self-consistent solution coincides with the one found previously for the structure.
Comparing the LSDA+ results for the undistorted and distorted unit cells, we can conclude that the charge-ordering pattern of and cations in the LT phase of , derived from the BVS analysis in [179] and confirmed by our study, is mainly forced by the local distortions of the crystal structure. The results of [155] consistently indicate the importance of the small amplitude of atomic displacements (almost of 0.07 Å) recently resolved by X-ray and neutron powder diffraction [111, 179]. The additional displacements leading to the supercell were estimated to be of ~0.01 Å but have not been fully resolved so far. They also may be important for full understanding of the CO in . In particular, in the subcell the true atomic positions are averaged over the corresponding number of subsites in the cell. Therefore, the actual arrangement of the locally octahedra in the true structure can be more complex, probably resulting in a more complicated charge and/or orbital order for the LT structure. The calculations in [155] indicate that the competition of the “elastic” and electrostatic energy contributions in the total energy appears to be responsible for the CO, which is realized in the LT structure of [181]. Because of this, the Verwey CO model, which has the lowest electrostatic but significant “elastic” energy contribution in the total energy, becomes less favorable than other arrangements.
3.2.4. Orbital Ordering
The self-consistent solution obtained by the LSDA+ is not only charge but also orbitally ordered. Table 1 clearly presents which presents the contribution of cubic harmonics to the formation of minority-spin states with an occupancy (next to last column in Table 1) evaluated by diagonalization of the corresponding occupation matrix self-consistently obtained by the LSDA+ [155].
As shown in the table the most occupied minority orbitals are centered on the , , and iron sites and have , , and characters, respectively. Remarkably, the occupied orbitals of cations are almost orthogonal to each other; that is, their relative orientation corresponds to an anti-ferro-orbital order. Since all cations are ferromagnetically coupled the obtained orbital order conforms with the anti-ferro-orbital ferromagnetic state, which is the ground state of the degenerate Hubbard model according to the Kugel-Khomskii theory [199, 200]. This orbital order is consistent with the corresponding distortions of FeO6 octahedra. In particular, using simple considerations which take into account only the change of the Fe–O bond lengths and neglect the bending of the bonds, it was previously concluded that the calculated orbital order is mainly determined by the distortions of oxygen octahedra surrounding sites [183].
Also this simple analysis shows a remarkable difference between and cations; namely, the average –O distance in the plane of occupied orbital is 2.087 Å, whereas in the planes of two other orbitals they are only 2.063 and 2.067 Å. This difference between the average cation-anion distance in the planes of occupied and unoccupied orbitals is remarkably larger for (more than 0.02 Å), although for they are 2.074 and 2.067 Å for occupied and unoccupied orbitals, respectively, which gives a difference of only 0.007 Å. This small difference can be changed by applying a uniaxial stress to the unit cell resulting in modification of the electronic properties [201]. In particular, a few percent of magnitude elongation of the unit cell along the -axis with simultaneous (in order to preserve the same unit cell volume) compression in the plane gives rise to orbital-order crossover on the site from a to a occupied orbital. At the same time the charge order and occupied orbitals on the sites remain the same. The pressure-induced spatial reorientation of the occupied orbital was proved by the LSDA+ calculations for the strained unit cell. Note, however, that these rough estimations do not take into account the elastic anisotropy in . Moreover, the analysis was performed for the “averaged” structure. However, they provide insight into the orbital-ordering phenomena behind the Verwey transition in magnetite as well as the problem of an external parameter-controlled electron state (e.g., orbital ordering) in solids [202].
3.2.5. Magnetic Moments
The strong variation of the occupancies of the minority-spin states leads to a pronounced modulation of the spin magnetic moments on the sublattice. While the total moment per formula unit remains at 4 , the magnetic moments of the (3.50 ) and (3.48 ) cations become appreciably smaller than (3.94 ) and (3.81 ) moments. The charge and spin modulation on the sublattice is accompanied by formation of a weak spin modulation on the oxygen ions caused by different strengths of the hybridization of O states with the minority-spin states of and ions. In particular, the oxygen magnetic moment reaches its maximal value of ~0.1 for O3 and O4 ions, which lie in the plane of cations. It substantially decreases for other oxygen ions and approaches minimum for O1 and O2 lying in the plane of cations (~0.04 ).
Recently, an anomalously large value of the orbital magnetic moment reaching 0.33 has been deduced by applying sum rules to experimental X-ray magnetic circular dichroism spectra of [203]. In addition, the unquenched orbital moment was also reported to be confirmed by the LSDA+ calculations. Later, however, this experimental finding was questioned by Goering et al. [204]. The average orbital moments between and were found from X-ray magnetic circular dichroism sum rules depending on the integration range. From the spin-polarized relativistic LSDA+ calculations [155] for the LT structure it was estimated orbital moments of and for and ions, respectively. Somewhat larger values of and were calculated for and cations, respectively. Taking into account the negative orbital moment of , this gives the value of for the average orbital moment. Thus, in agreement with the previous theoretical results of [10] and XMCD sum rule data of [204], the calculations give the value of Fe orbital moment of which is much smaller than reported in [203].
3.2.6. Exchange Coupling Constants
The calculations of the exchange interaction parameters were also performed [155] via the variation of the ground-state energy with respect to the magnetic moment rotation angle [205]. The exchange coupling parameter represents the effective pair exchange interaction between the th and th Fe atoms with effective Heisenberg Hamiltonian . Here, and are the spins at sites and (5/2 and 2 for and cations, resp.). Positive (negative) values of correspond to the ferromagnetic (antiferromagnetic) coupling between sites. As shown in Table 2 the exchange couplings between and iron sublattices are rather large, of about −70 K, and antiferromagnetic. The interactions are weakly antiferromagnetic with the maximal absolute value of 9.3 K (not shown in Table 2). The exchange couplings between the sites ( K) are substantially smaller than ones and almost all of them are ferromagnetic (see Figure 12). Weak antiferromagnetic couplings with K are also obtained (mainly between the sites with the same 2+ or 3+ valence state, shown by the thin (blue) lines in Figure 12). The spatial representation of these exchange couplings is presented in Figure 12. Other couplings that are not shown in Table 2 are weaker than 10 K.
Experimental estimation of the exchange couplings in was first performed by Néel on the basis of the two-sublattice collinear model [188]. From analysis of the temperature behaviour of the saturation magnetization and paramagnetic susceptibility, he obtained , , and K, where and refer to the tetrahedral and octahedral Fe sites, respectively. These values are qualitatively in accordance with the results presented in Table 2; namely, as in Neel’s model, the calculations result in strong antiferromagnetic coupling between the and sublattices; couplings (not shown in Table 2) are considerably smaller than ; the exchange couplings in the sublattice are weak and almost all of them are ferromagnetic. On the other hand, the small antiferromagnetic exchange interaction (see Table 2) is in exact agreement with recent estimations using the two-sublattice model [206]. Three-sublattice model calculations give an overall similar result, except, however, the exchange coupling, which seems to be overestimated [207].
3.2.7. Summary
The LSDA+ study of the model of the LT phase of [155] shows a charge- and orbitally ordered insulator with an energy gap of 0.18 eV. The obtained charge-ordered ground state is described by a dominant charge density wave with a minor modulation on the sublattice. A weak spin/charge modulation on the oxygen ions was also obtained. The CO coincides with the earlier proposed class I CO [111, 179] and confirms violation of the Anderson criterion [156]. While the screening of the charge disproportion is so effective that the total charge disproportion is rather small (0.23), the charge order is well pronounced with an order parameter defined as the difference of occupancies of 2+ and 3+ cations (0.7). This agrees well with the result of BVS analysis for a monoclinic structure (0.2). The orbital order is in agreement with the Kugel-Khomskii theory [199] and corresponds to the local distortions of oxygen octahedra surrounding sites.
Calculations of the effective exchange coupling constants between Fe spin magnetic moments show that the dominating interaction is an antiferromagnetic coupling between and moments. The coupling between and moments is found to be weaker and ferromagnetic.
3.3.
Iron borate () is a semivalent oxide. It belongs to the homometallic warwickite family with formal chemical formula , where and are, respectively, a divalent and trivalent metal ions. Surprisingly, the homometallic () warwickites are known only for Fe [208] and Mn [209]. In both compounds the metal has octahedral coordination. These octahedra share edges to form ribbons of four infinite along crystallographic direction chains of octahedra linked by corner sharing and the trigonal BO3 groups (see Figure 13).
There are two crystallographically inequivalent sites of the metal ions Fe(1) and Fe(2). is -type ferrimagnetic with drastically smaller in comparison with critical temperature of K, the Fe(1) magnetic moments being aligned antiparallel to the Fe(2) moments. It is almost antiferromagnetic, but a small ferrimagnetic moment of per Fe atom in a 0.05 T field was found [208]. At room temperature is a semiconductor with a thermoactivated conductivity below with eV [208]. Upon farther heating a broad semiconductor-to-semiconductor transition occurs at K, where resistivity drops down by a factor of , and, as a result, a small decrease of the activated energy up to eV above 350 K is observed [208]. The 317 K transition is assigned to charge ordering of 2+ and 3+ Fe cations on Fe(1) and Fe(2) sites, and accompanied by a structural transition from monoclinic to orthorhombic symmetry with increasing temperature. This structural transition is attributed by modification of the angle from at 3 K to at 337 K [208]. The change in conductivity and structure are small. But the Mössbauer spectra at around 317 K clearly result in the charge localization at the transition with an equal distribution of and cations over the two structurally distinct Fe(1) and Fe(2) sites with formal chemical formula [208, 210]. Although, there are two types of distorted FeO6 octahedra with Fe–O bond length varying between 1.92 and 2.23 Å for 3 K, the average Fe(1)–O and Fe(2)–O distances are 2.085 and 2.082 Å, respectively, that is, equal within experimental errors [208]. Such a small difference results in the extremely small value of deviation (≤0.01) from the average 2.5+ value of valence of Fe cations estimated by the bond valence sum method. While an electronic transition between charge-ordered and charge-disordered states occurs at around 317 K, as evidenced by the Mössbauer spectroscopy and resistivity measurements, no long-range ordering is directly observed by X-ray, neutron, or electron diffraction. Thus, a long-range charge ordering such as the simple alternating scheme proposed in [208] destroys the mirror symmetry, which leads to a tilting of the Fe ribbons, consistent with the observed enlargement of the angle below the transition. However, there is no observation of the increasing of -axis periodicity (it should increase by a factor of two or another integer factor below ). Thus, below the transition, a charge ordering is not implicit in the atom coordinates, although it is indirectly evidenced by other experiments. This ambiguity is resolved in our electronic structure study, which reveals an arrangement of and cations alternately ordered within the chains along the direction.
Theoretical investigation of the electronic structure and magnetic properties of in the low-temperature structure was reported in [211]. An order parameter, defined as the difference between minority-spin occupancies of and as well as the difference between majority-spin occupancies of and cations was propose. This order parameter was found to be quite large, although the total charge difference between 2+ and 3+ cations is small.
The band structure calculations have been carried out for the low-temperature monoclinic structure of . The corresponding unit cell contains four formula units. The LSDA calculations give only a metallic ferrimagnetic solution without charge separation where partially filled bands at the Fermi level originate from the orbitals of Fe cations (see Figure 14).
The lower part of the valence band (below −3.5 eV) is mainly formed by O states with a bonding hybridization with Fe states. Fe states give predominant contribution to the bands at −3.5 eV below and up to 2.5 eV above the Fermi level. The exchange splitting between the spin-up and spin-down Fe states is roughly 3 eV which results in a net magnetic moment of 0.31 per formula unit. Additionally, the fivefold levels are split by the crystal field into and subbands. The oxygen octahedra in are strongly distorted and the local symmetry of Fe sites is, of course, lower than cubic. Nevertheless, the cubic component of the ligand field, which is determined by the relative strength of hybridization of - and -type, remains dominant, whereas the splitting within “” and “” subbands is smaller than the corresponding band-width. This allows one to label the corresponding states as and . The crystal-field splitting is roughly 2 eV, which is less than the exchange splitting. This is consistent with the high-spin state of the Fe cations. The symmetry inequivalence of Fe(1) and Fe(2) sites leads to an inexact cancellation of magnetic moments and results in a small ferrimagnetic moment of per formula unit.
Fe(1) and Fe(2) and states with the opposite spin projections share nearly the same energy intervals. Thus, Fe states between −3.5 and −2.0 eV originate predominantly from majority-spin Fe(1) and minority-spin Fe(2) states whereas the states between −2.0 and −0.5 eV are mainly of character. Partially occupied bands crossing the Fermi level are formed by minority spin Fe(1) and majority-spin Fe(2) states. The nominal occupation of these bands is 1/6. In the majority-spin channel, however, the Fe(2) state, which is oriented in the plane perpendicular to the shortest Fe(2)–O bond, forms quasi-one-dimensional bands with a strong dispersion along the direction. The one-dimensional character of the dispersion is determined by the existence of only two nearest neighbours of the same kind around each Fe(2) ion. The other two Fe(2) states are shifted to higher energy and the corresponding bands are completely unoccupied. As a result, the majority-spin bands crossing the Fermi level turn out to be half filled.
An Fe(1) ion, in contrast to Fe(2) one, has four Fe(1) neighbours at close distances. As a result of the hybridisation between Fe(1) states the situation in the minority-spin channel is more complicated. Twelve bands are split into three groups of 4 bands each. The Fermi level is crossed by lowest bands which show a rather strong dispersion along but with a two times smaller period.
It should be noted that in contrast to experimental data [212] LSDA predicts to be metallic with substantial magnetic moment per unit cell. Apparently, the electron-electron correlations, mainly in the shell of Fe cations, play a significant role.
The LSDA+ calculations have been performed for the unit cell as well as for double () and triple () supercells of (without putting in any local displacements of oxygen atoms around / sites). Thus, for the CO pattern proposed in [208] using the classical value of Coulomb and exchange interaction parameters for Fe 5 eV and 1 eV, respectively, a charge-ordered insulator with an energy gap of 0.13 eV was found. This is in a strong contrast with metallic solution without CO obtained by the LSDA. This is a notable result because a CO is not implicit in the atom coordinates, and it shows that LSDA+ calculations can assist experiments in revealing CO arrangements. To obtain a reasonably good agreement of the calculated gap of 0.39 eV with experimental value of 0.35 eV, the value has to be increased up to 5.5 eV (see Figures 15 and 16). It does not exceed 10% of the value, which is in an accuracy of the calculation. Note, however, that the CO obtained by LSDA+ within supercell does not depend on the value of 5–5.5 eV. Here and in the following all results are presented for double along -direction supercell of .
After self-consistency each of two groups of Fe(1) and Fe(2) atoms is split out in two subgroups of 2+ and 3+ Fe cations with equal number of 2+ and 3+ cations. Thus, one of majority-/minority-spin states of Fe(2)/Fe(1) atom becomes completely occupied, whereas all the rest of states are pushed by strong Coulomb interaction at the energies above 3 eV. The gap is opened between occupied and unoccupied states of and for spindown and and for spinup. Majority-spin states of and minority-spin states of cations are shifted below the states, which form the band in the energy range of −8 and −2 eV. In contrast to states, the majority-spin and minority-spin states form the broad bands between −8 and −1 eV.
The obtained magnetic structure is almost antiferromagnetic (without spin moment per unit cell) with nearly the same spin moment per and as well as per and cations. Using the moment populations in Table 3, the calculated net moment is per Fe atom, in exact agreement with the experimental value [208].
The charge order obtained by LSDA+ in supercell is consistent with observed enlargement of the angle below the transition and coincides with charge-ordering scheme proposed earlier by Attfield et al. [208] It is described by the sloping 2+ and 3+ Fe cation lines alternately stacked along direction and could be considered as a quasi-one-dimensional analog of the Verwey CO model in pyrochlore lattice of . An additional self-consistent LSDA+ calculations for unit cell as well as for double and triple along direction supercells was performed using the same and values. But only self-consistent solutions with larger value of the total energy or with substantial magnetic moment per unit cell, which contradicts the experimental data, were found. Also it was found that other charge arrangements in supercell are unstable, and the stable one coincides with the CO found previously. Thus, the CO obtained for certain value of and does not depend on the initial charge arrangement. It is not possible to check all possible CO arrangements including more complex CO scenarios, but our results consistently indicate that the obtained CO solution is more favourable than other simple alternatives and is the ground state of in the low-temperature phase.
Although the corresponding total charges difference and disproportion of the total electron charges inside the atomic spheres of and cations are small, an analysis of occupation matrices of Fe(1)/Fe(2) minority-/majority-spin states confirms substantial charge disproportionation. Thus, as shown in Table 3, one of the states of and cations is almost completely filled with the occupation numbers , whereas the remaining two orbitals of the cations have significantly smaller population of about 0.1. According to [181] an order parameter was defined as the largest difference between and populations. While, due to strong static “screening” effects, the order parameter introduced as the total charge difference between 2+ and 3+ Fe cations is ill defined, the well-defined order parameter is the difference of occupancies for and cations, which amounts to 80% of ideal ionic CO model and clearly pronounces the existence of CO below the transition. The occupation matrices analysis shows that the change of the occupations caused by the charge ordering is very effectively screened by the rearrangement of the other Fe electrons. Thus, significant contribution to the charge screening is provided by Fe states due to relatively strong bonds with O states and, as a result, appreciable contribution to the occupied part of the valence band.
The occupied states of cations are predominantly of character in the local cubic frame (according to that we later mark the orbital as orbital). This is illustrated in Figure 17, which shows the angular distribution of the majority and minority spin electron density of the Fe(2) and Fe(1) cations, respectively. Thus, occupied and unoccupied cations are ordered alternately within the chain which is infinite along direction. The angular distribution of charge density of the Fe(1) and Fe(2) cations, which correspondingly belongs to different Fe ribbons being formed a cross in the structure projected on (100) plane (see Figure 13), is shown in Figure 18.
Using the LSDA+ method the exchange interaction parameters have been calculated via the variation of ground-state energy with respect to the magnetic-moment rotation angle [211]. In Table 4 we have shown the total set of different intraribbon exchange parameters as well as a contribution of different subbands into exchange interactions. The spatial representation of all these exchanges is schematically presented in Figure 19. Surprisingly, only the exchange interaction parameter between and cations is ferromagnetic with relatively small value of K. In contrast, the nearest sites in quasi-one-dimensional Fe(1) chain are coupled antiferromagnetically with noticeably larger exchange absolute value of K. Furthermore, the exchange parameters between the nearest sites of two Fe(1) chains are relatively strong and antiferromagnetic (see , , and in Table 4). Therefore, the Fe(1) sublattice is highly frustrated, while the relatively weak frustrations in the Fe(2) sublattice considerably reduce ferromagnetic interaction within Fe(2) chain. Also it is interesting to note that relatively strong ferromagnetic intrachain interaction between subbands of and cations (see in Table 4) is strongly suppressed by the substantial antiferromagnetic and exchange.
On the other hand, the interribbon exchange interaction parameters between Fe(1) and Fe(2) atoms are considerably larger. The values of these interactions are shown in Table 5, whereas the spatial representation is schematically presented in Figure 20. Thus, the exchange parameters between and cations are antiferromagnetic with values of K and K (see Table 5). Such an appreciable difference between and arise from geometry. Thus, the former corresponds to the exchange interaction between Fe(1) and Fe(2) atoms, which belongs to an edge, whereas the latter corresponds to the diagonal interaction. It seems that such geometrical reason is also responsible for decrease of absolute value of the exchange interactions between and cations from K to K (see Table 5). Also it is interesting to note that the exchange interaction between and cations are considerably larger than between and ( and , correspondingly). We find that the interribbon exchange interactions play predominant role and determine the whole -type ferrimagnetic spin structure below in contrast with the ferromagnetic intrachain order due to superexchange [208].
3.3.1. Summary
In the LSDA+ study of the low-temperature phase of [211] was found a charge-ordered insulator with an energy gap of 0.39 eV. While the screening of the charge disproportion is so effective that the total charge disproportion is rather small (0.34), the charge order is well pronounced with an order parameter defined as a difference of occupancies of 2+ and 3+ Fe cations (0.8). The occupied and cations are ordered alternately within infinite along -axis chains of Fe atoms. This result is remarkable in view of the absence of directly observed CO atomic displacements in the experimental coordinates and demonstrates the utility of the LSDA+ method as an aide to experimental studies of CO structures. However, the charge order obtained by LSDA+ is consistent with observed enlargement of the angle and coincides with charge-ordering scheme proposed earlier by Attfield et al. [208]. It seems certain that is charge ordered below , and the absence of the long-range charge ordering from X-ray, neutron, or electron diffraction arises from formation of charge order within small domains, which have been termed “Wigner nanocrystals” [213]. Thus, the superstructure peaks are too weak and broad to be observed against background in diffraction patterns, whereas the observed long-range monoclinic lattice distortion can arise despite a large concentration of defects as these preserve the direction of the monoclinic distortion but do not propagate the coherent doubling of the lattice periodicity. An analysis of the exchange interaction parameters obtained by LSDA+ method inevitably results in predominance of the interribbon exchange interactions which determine the whole -type ferrimagnetic spin structure below , in contrast with the ferromagnetic intrachain order due to superexchange proposed earlier in [208].
4. Titanium and Vanadium Oxides
4.1.
The aforementioned phenomena of sharp metal-insulator transitions associated with pronounced charge and/or orbital ordering are characteristic for the Magnéli phases (). These compounds form a homologous series and have been studied recently to understand the differences in crystal structures and electronic properties between the end members () and () [214]. In particular, the metal-insulator transition of discovered some fifty years ago still is the subject of ongoing controversy and is another “hot topic” in solid-state physics. LSDA calculations have revealed strong influence of the structural degrees of freedom on the electronic properties of and neighbouring rutile-type dioxides [215–217]. In this scenario the characteristic dimerization and antiferroelectric displacement of the metal atoms translate into orbital ordering within the states and a Peierls-like singlet formation between neighbouring sites. Recently, this was confirmed by LDA+DMFT calculations, which suggested to regard the transition of as a correlation-assisted Peierls transition [218].
titanium oxide is another remarkable member of the Magnéli phases with which shows metal-insulator transitions associated with the spatial charge ordering. It is a mixed-valent compound which has an even mixture of 3+ and 4+ Ti cations (), corresponding to an average occupation of 1/2 electron per Ti site. Electrical resistivity, specific heat, magnetic susceptibility, and X-ray diffraction data reveal two first-order transitions in the temperature range of 130–150 K [219]. At 150 K a metal-semiconductor transition occurs without measureable hysteresis in resistivity and specific heat. It is followed by a semiconductor-semiconductor transition at 130–140 K, which again is characterized by an almost two orders of magnitude abrupt increase in electrical resistivity and has a hysteresis of several degrees [219]. The magnetic susceptibility shows a sharp enhancement when heating through 150 K. However, it is small and temperature independent below this temperature and does not show any anomaly at 140 K.
The crystal structure of (see Figure 21) can be viewed as rutile-type slabs of infinite extension and four Ti sites thickness, separated by shear planes with a corundum-like atomic arrangement. Below 130 K it crystallizes in a triclinic crystal structure with two formula units per primitive unit cell [220]. Four crystallographically inequivalent Ti sites are found at the centers of distorted oxygen octahedra. They form two types of chains, namely, (a) 1-3-3-1 and (b) 2-4-4-2, which run parallel to the pseudo-rutile -axis and are separated by the crystallographic shear planes. Although interatomic distances in the (b) chain are almost uniform (3.01 and 3.07 Å between 4-4 and 2-4 Ti sites, resp.) they are remarkably different for the (a) chain (3.11 and 2.79 Å between 3-3 and 1-3 Ti sites).
Accurate determination of the crystal structure allowed to elucidate the nature of the three phases distinguished by the two first-order transitions [220]. In particular, in the metallic phase the average Ti–O bond lengths for crystallographically inequivalent TiO6 octahedra are very similar which results in the average valence state of 3.5+ per each Ti cation. Below 130 K charge has been transferred from the (b) to the (a) chains. In addition, cations in alternate (a) chains are paired to form nonmagnetic metal-metal bonds, whereas in the intermediate phase pairing also persists but its long-range order calls for a fivefold supercell [219]. Thus, the 130–140 K transition is associated with a transition to the phase with a long-range order of - pairs, whereas above 150 K 3+ and 4+ Ti cations are disordered. The presence of the - pairs strongly differentiates from and results in two steep first-order transitions found in the electrical resistivity.
Recent LSDA band structure calculations of both high- and low-temperature phases of results in significant charge separation between crystallographically independent 3+ and 4+ Ti sites in the low-temperature phase, whereas a rather isotropic occupation of the states has been found at room temperature [221]. While, in addition, an orbital order at the Ti chains originating from metal-metal dimerization was found, the LSDA gave only metallic solution with semimetallic-like band overlap instead of the semiconducting gap. This problem is overcome in our work taking into account strong electronic correlations in Ti shell using the LSDA+ method.
In [187] the authors investigate the electronic structure of the low-temperature phase using the LSDA+ approach. The LSDA+ calculations result in a charge- and orbitally ordered insulator with an energy gap of 0.29 eV, which is in a good agreement with an experimental gap value of 0.25 eV. From the results of [187], an orbital-order parameter was proposed as the difference between majority-/minority-spin occupancies of and cations respectively. This order parameter is found to be quite large, although the total charge difference between 3+ and 4+ cations, remains small. Also it is interesting to note that the total charge separation between 3+ and 4+ Ti cations is completely lost due to efficient screening by the rearrangement of the other Ti electrons. In addition, we find a strong antiferromagnetic coupling of K of the local moments within the dimerized - pairs, whereas an interpair coupling is only of ≈40 K. This is in a good agreement with small and temperature-independent magnetic susceptibility in the low-temperature phase of .
4.1.1. LSDA Band Structure
The LSDA band structure calculations [187] for the low-temperature structure gives a nonmagnetic metallic solution with substantial charge separation between crystallographically independent Ti(1)/Ti(3) and Ti(2)/Ti(4) cations. The lower part of the valence band below −3 eV is predominantly formed by O states with a bonding hybridization with Ti states. Crystal -field splitting of the latter is roughly of 2.5 eV. Ti states form the group of bands at and up to 2 eV above the Fermi energy, whereas Ti states give a predominant contribution to the bands between 2.5 and 4.5 eV. Within the group of bands, the symmetry inequivalence of Ti(1)/Ti(3) and Ti(2)/Ti(4) sites leads to substantial charge separation between these two groups of Ti atoms. In addition, an analysis of the partial density of states reveals significant bonding-antibonding splitting of (in local cubic frame) states of about 1.5 eV for Ti(1)/Ti(3) cations, whereas Ti(2)/Ti(4) cations show a relatively weak substructure. This substantial bonding-antibonding splitting of Ti(1)/Ti(3) states agrees well with the concept of formation of - spin-singlet pairs proposed earlier by Lakkis et al. [219]. However, the LSDA calculations fail to reproduce an insulating spin-singlet ground state of the low-temperature phase of . Apparently, the electron-electron correlations, mainly in the shell of Ti cations, play a significant role.
4.1.2. LSDA+ Results and Charge Ordering
In order to take into account strong electronic correlations in Ti shell, authors of [187] perform LSDA+ calculations for in the low-temperature structure. The LSDA+ calculations result in a charge and orbitally ordered insulator with an energy gap of 0.29 eV (see Figure 22). This is in a strong contrast with the metallic solution with a substantial charge disproportionation between crystallographically inequivalent Ti(1)/Ti(3) and Ti(2)/Ti(4) cations obtained by LSDA and in a reasonably good agreement with an experimental gap value of 0.25 eV. Note, however, that the charge- and orbital-order pattern remains exactly the same for in the range 2.5–4.5 eV, whereas the energy gap increases considerably up to 1.12 eV for eV. This remarkable increase of the gap value is accompanied by the enhancement of the spin magnetic moment from 0.56 up to 0.8 per 3+ Ti(1)/Ti(3) cation as is increased from 2.5 to 4.5 eV.
In addition, authors perform LSDA+ calculations for high-temperature metallic phase of [187]. In particular for of 2.5 eV a metallic self-consistent solution with substantial density of states (76 states/Ry) at the Fermi level has been found, whereas for of 3 eV the LSDA+ solution becomes unstable but remains metallic. With further increase of the value the metallic solution collapses into insulating one.
After self-consistency four crystallographically independent Ti atoms are split out in two subgroups with respect to the spin magnetic moment per Ti site: Ti(1)/Ti(3) with a moment of 0.66/−0.67 , respectively, and Ti(2)/Ti(4) with 0.04/−0.02 . Thus, one of majority-/minority-spin states of Ti(1)/Ti(3) becomes occupied , whereas all other states are pushed by strong Coulomb interaction above the Fermi level. In contrast, all states of Ti(2) and Ti(4) are almost depopulated and form bands up to 2.5 eV above the Fermi level. The occupied Ti(1)/Ti(3) states are strongly localized and form a prominent structure with a bandwidth of 0.25 eV just below the Fermi level (see Figure 23). The strong Coulomb interaction does not affect much the empty Ti states, which give predominant contribution between 2.5 and 4.5 eV. The obtained magnetic structure is almost antiferromagnetic with the spin magnetic moments within - as well as - pairs being of the same magnitude with opposite sign.
An analysis of occupation matrices of majority/minority spin states confirms substantial charge disproportionation within the Ti shell. As shown in Table 6, one of the states of cations is occupied with the occupation number of 0.74, whereas the remaining two orbitals have a significantly smaller population of about 0.08. Thus, according to [181] we define an orbital-order parameter as the largest difference between 3+ and 4+ Ti populations which amounts to 66% of ideal ionic charge-ordering model. The orbital-order parameter clearly shows the existence of substantial charge disproportionation in the Ti shell of which is remarkable because of the complete lack of the total charge separation (see column in Table 6) between 3+ and 4+ Ti cations. The occupation matrices analysis shows that the change of the occupations is very efficiently screened by the rearrangement of the other Ti electrons. A significant portion of the screening charge is provided by Ti states due to formation of relatively strong bonds with O states, which results in appreciable contribution of the former to the occupied part of the valence band. Ti and states give additional contributions to the screening of the difference in occupations which leads to complete loss of the disproportionation between the charges at 3+ and 4+ Ti sites.
The occupied states are predominantly of character in the local cubic frame (according to that we later mark the orbital as orbital). This is illustrated in Figure 24, which shows the angular distribution of the majority- and minority-spin electron density of Ti cations, marked by red and cyan color (or light and dark on the black and white image), respectively. Since and cations are antiferromagnetically coupled, the obtained ferro-orbital order is consistent with the formation of a bonding spin-singlet state from the orbitals of two neighboring Ti(1) and Ti(3) sites. The orientation of occupied orbitals is consistent with the largest average Ti-O distance in the plane of orbitals. As shown in Table 7 the average Ti(1)–O distance (2.061 Å) in the plane of orbital is considerably larger than average distances in the other two and planes (2.032 and 2.045 Å, resp.). The same is also true for the Ti(3) cation but in this case the variation of the average Ti(3)–O distances is much smaller (2.047 versus 2.041 and 2.042 Å), and, as a consequence, the out-of-plane rotation of the occupied minority spin orbital is stronger.
In addition, hopping matrix elements were evaluated via Fourier transformation from reciprocal to real space of the Ti LSDA Wannier Hamiltonian [222]. Remarkably, for the low-temperature phase the Ti(1)-Ti(3) intra-pair - hopping matrix element is found to be of 0.61 eV, whereas all other hoppings are 3-4 times smaller. This strong inhomogeneity of the hopping matrix elements disappears in the high-temperature phase. Thus, according to our calculations hopping elements in the high-temperature phase are 0.23, 0.21, 0.39, and 0.33 eV between 1-3, 2-4, 3-3, and 4-4 Ti sites, respectively.
Estimation of exchange interaction parameters via the variation of the ground-state energy with respect to the magnetic moment rotation angle [17] results in a strong antiferromagnetic coupling of −1696 K between and cations. All other couplings are two orders of magnitudes smaller. This indicates a possible formation of the spin-singlet pairs via direct antiferromagnetic exchange between neighboring Ti(1) and Ti(3) sites. The contribution of the superexchange via O orbitals to the Ti(1)-Ti(3) exchange coupling is found to be negligible. This was verified by calculating the exchange coupling constants with the subblocks of the LMTO Hamiltonian responsible for the Ti-O hybridization being set to zero. This calculation gave qualitatively same results for the exchange constants although the possibility for the superexchange via O orbitals was eliminated.
4.1.3. Summary
In the study [187] of the low-temperature phase of show a charge-ordered insulating solution with an energy gap of 0.29 eV. The total charge separation is small (less than 0.14), whereas the orbital-order parameter defined as the difference between occupancies of and cations is large and gives direct evidence for charge ordering. Ti and states give a strong contribution to the static “screening” of the total charge separation. This effective charge screening leads to complete loss of the disproportionation between the charges at 3+ and 4+ Ti sites which is in remarkable contrast with one finding in and [183]. The occupied states of cations are predominantly of character (in the local cubic frame) and form a spin-singlet molecular orbital via strong direct antiferromagnetic exchange coupling between neighboring Ti(1) and Ti(3) sites of K, whereas the role of superexchange is found to be negligible. This is in a good agreement with small and temperature independent magnetic susceptibility in the low-temperature phase of .
4.2.
Among other transition metal oxides vanadates have recently attracted special attention due to the observation of the low-temperature behavior typical for “heavy-fermion” compounds in [119] and a spin-Peierls (SP) like transition in [223]. From the superstructure formation which gives rise to additional X-ray reflections at and a drop of the susceptibility below K, it was concluded that - is the second inorganic SP compound after CuGeO3 [224] with the highest transition temperature yet observed. In accordance with the original structure analysis [225], the existence of two sets of inequivalent () and () sites already above was assumed, and the transition was supposed to be due to singlet formation leading to a dimerization of spin- chains along the axis.
Further investigations have shown, however, that the compound does not undergo a conventional SP transition. X-ray diffraction experiments [226, 227] revealed that above has a centrosymmetric structure with one type of V site rather than noncentrosymmetric one as it was previously supposed. This implies that the high temperature phase is a mixed-valence compound and the average oxidation state of V ions is . Furthermore, only one set of equivalent magnetic V sites is observed in NMR measurements [228, 229]. On the other hand, these experiments show that below there exist two inequivalent and sites which can be explained by assuming that a charge-ordering (CO) transition occurs in . Thermal-expansion and specific-heat measurements [230] also provide evidence for two almost coincident phase transitions around . The appearance of superimposed CO and SP transitions has been proposed within a theoretical model in [231].
Different models for the CO phase which account for spin gap formation have been proposed [231–233]. Although the low-temperature crystal structure is known by now [234], the associated CO model has not yet been determined unambiguously. Relevance of such a model can be verified by comparison of the calculated dispersion of magnetic excitations with the experimental one. Previous neutron scattering data [235] did not yet allow to distinguish between different possibilities; more recent experiments with higher resolution have improved this possibility. The spin excitation spectra were discussed in [236]. It should be noted that the theoretical spectra are rather sensitive to the actual values of exchange constants and their reliable determination is a very important and challenging task.
The electronic structure of was intensively studied experimentally by means of optical absorption [237] and reflectivity [238, 239] as well as theoretically, based on band structure calculations [227, 240–242]. However, there is a controversial discussion about the origin of the electronic excitations. Concerning the absorption peak occurring at about 1 eV, transitions between bonding and antibonding combinations of V states [227, 238, 243], and transitions between vanadium states of different symmetry [239] as well as on-site d-d transitions between crystal-field-splitted vanadium states [237] are proposed as a source. Furthermore, the information from the experiments appears to be insufficient in order to find a unique parameter set for the description of the electronic structure in .
4.2.1. Structure
crystallizes in an orthorhombic unit cell with the lattice constants Å, Å and Å [244]. The vanadium atoms and their five nearest neighbored oxygen atoms build slightly distorted VO5 pyramids which are connected by their corners along the direction as well as by their corners and edges along the a direction as shown in Figure 25(a). The resulting pyramid layers in the -plane are separated by sodium atoms. The weak bonds between the vanadium oxide layers and the sodium layers are the reason for the good cleavage behavior in the plane perpendicular to the direction. The projection of the vanadium and the oxygen atoms of a single pyramid layer onto the -plane, excluding the oxygen atoms on the tips of the pyramids, delivers the atomic configuration as illustrated in Figure 25(b). This approach points up the ladder structure in which adjacent ladders are shifted by half of the lattice parameter b in the b direction (see dashed lines in Figure 25(b)).
(a)
(b)
4.2.2. LDA Bands and TB Parameters
The calculated LDA band structure and total DOS of are presented in Figure 26. The lower part of the valence band is formed mainly by O states with a bonding hybridization with V states. It is separated by a gap of ≈3 eV from the bottom of V states which give predominant contribution to the bands at and up to ≈4 eV above the Fermi level. It should be noted that in contrast with experimental data LDA predicts to be metallic.
Contributions from states of different symmetry () to the density of V states are shown together with the density of O states in Figure 27 [245]. Compare again Figure 28 for the orientation of the relevant orbitals with respect to the lattice, in particular the vanadium-oxygen -plane. The two V bands crossing the Fermi level and the next two less than one eV above are formed mainly by V states with states giving significant contribution to the upper two. In a simplest tight-binding (TB) model which takes into account only the hybridization of V states with states of the nearest O atoms and neglects the distortion and tilting of the VO5 pyramid, the V orbital forms bonds with the orbital of the atom and orbitals of the atoms in the base of the pyramid and does not hybridize with the nearest to V apex oxygen ( above and below the drawing plane of Figure 28). The states in the energy range 1-2 eV are mainly of V character. They are shifted to higher energy relative to V states by a small contribution of antibonding hybridization with orbitals of the O atoms forming the base of the pyramid, which is due to a small displacement of the V ions out of the basal plane of the pyramid. Finally, the bands above ≈2 eV originate from V and states which form antibonding states with and orbitals, respectively. It is interesting to note that this picture of the chemical bonding in - with the bands crossing the Fermi level formed by relatively weakly hybridized V states is in some sense complementary to the case of layered cuprates where the highest occupied states originate from strongly anti-bonding Cu –O states of character. Here, the V ion resides in the interior of a pyramid whose basal square has its diagonals in and directions and whose apex is on the -axis. Four of the five -orbitals of vanadium can make bonds partially of -character with -orbitals of oxygen ions at the corners of the pyramid, except for the -orbital, which for symmetry reasons can only make -bonds. Hence, we have -bands around the Fermi level in an ionicity gap of -bands, and vanadates are -electron systems. This explains the small bandwidths already on the mean-field level.
The two pairs of bands formed by V are of key importance for understanding the electronic properties of . These bands are separated by a small gap of ≈0.2 eV from the higher bands with the splitting between the pairs being eV (see Figure 26). The two bands crossing the Fermi level exhibit rather strong dispersion along Γ-Y direction and to a lesser extent along Γ-X, whereas the other two bands are almost dispersionless. All four bands show no appreciable dispersion along Γ-Z direction.
An effective TB model constructed so as to reproduce the calculated band structure is a very useful tool which helps to understand the details of the chemical bonding and can be used as a basis for construction of more involved many-body Hamiltonians. Such a TB model for the four lowest-lying V bands in was proposed in [227]. This simple model written in terms of effective V-V hopping integrals reproduces well the dispersion of the lower pair of the bands and the average splitting between the pairs. However, it fails to account for the strongly suppressed dispersion of the upper two bands along Γ-Y direction. Also, the model contains the hopping terms between rather distant V atoms, and it is difficult to estimate in advance which of these terms should be included in the model.
As follows from the analysis of DOS (Figure 27) and the LMTO eigenfunctions, relevant for the TB model are V , , and orbitals. To distinguish between two types of atoms surrounding a V site, we shall use where necessary the notation for the oxygen atom lying at the continuation of the –– rung whereas the atoms placed along the V chain running along direction will be still denoted as . With the appropriate choice of a unit cell neither of V bonds crosses the cell boundary and the orbitals can be excluded from the model, their effect being taken into account implicitly via renormalization of remaining hopping terms. In other words in our model is the antibonding V molecular orbital (MO) rather than atomic-like V orbital.
The dispersion of the lower pair of V bands can be reproduced already within the TB model which includes only four hopping matrix elements (see Figure 29(a)). Strong V hybridization (eV) is responsible for the splitting of the four bands into two subbands. The dispersion along Γ-Y direction is due to V hopping (eV), whereas the band crossing in this direction is provided by the direct -hopping between orbitals (eV). Finally, the small matrix element eV between V orbitals governs the dispersion along Γ-X direction. As was mentioned above we assume in the model that is an antibonding V MO and the effective term includes not only direct hopping but also the hopping term of the same sign between orbitals participating in the MO. Moreover, as atoms are slightly shifted away from the V chains running along direction the hopping terms between V orbital and orbital of atoms from the same chain give nonvanishing contribution to . The sign of this term is determined by the direction of the out-of-chain displacement of atoms. For the experimentally observed displacement toward the V atom from another ladder the sign is opposite to the sign of the direct hopping, thus decreasing the effective .
To verify whether the compensation of the individual contributions to really occurs, the calculations with an enlarged out-of-chain displacement of atoms along direction was performed. As a result of the shift and distances decrease by 1.5% and 1.8%, respectively, while the V–V distances remain unchanged. If the V hybridization was weak, one would expect a small increase of the splitting of the lower pair of V bands at the Γ point due to stronger hopping. The calculated splitting decrease, however, from 0.15 eV for the original structure to 0.08 eV for the distorted one indicating that the effective is very sensitive to the relative position of V and atoms.
As can be seen from Figure 29(a) the TB model with the four hopping terms gives nearly the same dispersion for both lower and upper pairs of the V bands, and additional hopping terms should be included to reproduce the flatness of the upper bands. We found that their strong dispersion along Γ-Y direction can be suppressed (see Figure 29(b)) by “switching on” (eV) and ( eV) hybridizations, both at least in part of -character. As the effect of both of these terms on the dispersion is similar, the values of and were determined using their ratio estimated from the distances between the corresponding oxygen atoms and the mutual orientation of the orbitals. The remaining dispersion of the upper pair of bands along Γ-X is canceled by the hopping term eV between the V MO and orbital of the atom from another ladder.
The dispersion of the lower pair of the V bands is not affected by the three above-mentioned hopping terms as all of them act via orbitals which give only a small contribution to the corresponding wave functions. The analysis of the eigenfunctions shows that at the Γ point the V orbitals centered at the ends of a rung have the same phases and, consequently, they are orthogonal to the orbital. At the arbitrary point the orthogonality is not perfect due to the weak interladder coupling along direction, but as the corresponding hopping term is very small the contribution of orbitals to the wave function remains negligible. On the contrary, the orbitals contribute strongly to the wave functions of the upper pair of the V which are -antibonding with respect to V hybridization.
The conclusion can be derived that these additional hopping terms are not important when describing the low-energy electronic excitations in . This is true, however, only for the high-temperature phase in which all V sites are equivalent. Below when and ions can occupy different ends of the same rung, the contribution to the wave functions corresponding to the lowest V bands can be substantial and the dispersion of these bands will be determined to a great extent by the hopping terms in which the orbitals are involved.
Figure 29(b) shows that the proposed extended TB model reproduces the dispersion of all four V bands [245]. The hopping terms obtained from comparison of this model to a TB model written in terms of effective V–V interactions are close to those given in [227]. An important difference is the appearance of an additional hopping term eV which couples orbitals of V atoms placed at the opposite ends of consecutive rungs of a ladder. This term has been found to be of the same absolute value as the hopping along the leg of a ladder but of the opposite sign and is necessary to compensate the dispersion of the upper pair of bands along Γ-Y direction produced by the later. As both and give the contribution of the same sign to the dispersion of the lower bands, we have obtained the value of eV which is two times smaller compared to the value of −0.17 eV found in [227]. It should be pointed out that the comparatively large can be responsible for exchange coupling of ions along the direction which is necessary to explain the strong dispersion of magnetic excitations along Γ-Y direction in the case of the ordering of into zigzag chains which is considered as a possible low-temperature structure of .
4.2.3. LDA+ Results
The electronic structure of the low-temperature phase of was studied using the LDA+ approach [245]. We restricted ourselves to consideration of CO structures which are possible in the unit cell doubled along the -axis, thus neglecting the experimentally observed increase of the unit cell along and axes. The lattice distortion caused by CO was not taken into account and the atomic positions determined for the high-temperature phase [226] were used. The LDA+ calculations were performed using the value of 3 eV for . The values of screened on-site Coulomb eV and exchange eV integrals were determined from supercell calculations. The calculated is significantly smaller than eV used for ions in in [240] which can be explained by the fact that in the super-cell calculations V and orbitals which form rather strong bonds with O orbitals were allowed to participate in the screening of excessive V charge, thus providing more perfect screening compared to the case when all V electrons are treated as localized [246].
The electronic structure and total energies were calculated for two models for the CO phase which have commonly been considered as possible candidates for the low-temperature structure [245]. In the first model (Figure 30(a)) magnetic ions form in-line chains along direction separated by nonmagnetic chains of ions. The second one (Figure 30(b)) consists of zig-zag chains of ions occupying alternating ends of consecutive rungs of a ladder. For each of these models different kinds of magnetic ordering of moments were considered.
(a)
(b)
The band structure and the total DOS for the model with the in-line CO and antiferromagnetic (AF) ordering of magnetic moments along the chains (cf. Figure 30(a)) are shown in Figure 31(a). The two highest occupied bands which are doubly degenerate due to AF order are formed by orbital combinations of the four ions, the states with opposite spin are pushed to higher energies by the on-site Coulomb repulsion . These almost dispersionless bands are ≈2 eV above the Fermi level and separated by an energy gap of ≈1 eV from the lowest unoccupied band. In the case of ferromagnetic (F) intrachain ordering and AF ordering along direction (Figure 31(b)) the hybridization between orbitals along the chains via orbitals leads to appearance of relatively strong dispersion along Γ-Y direction. As a result of the band broadening the correlation gap decreases to 0.7 eV.
(a)
(b)
The dispersion of the highest occupied and the lowest unoccupied bands calculated for the zig-zag CO model with either AF (Figure 32(a), spin pattern of Figure 30(b)) or F (Figure 32(b)) ordering of magnetic moments along the zig-zag chains is very similar to that obtained for the corresponding cases within the in-line CO model. These results illustrate the importance of the above mentioned effective hopping matrix element which couples orbitals of V ions occupying the opposite ends of consecutive rungs of a ladder. As in the CO phase the V ions at the ends of a rung are no longer equivalent, in contrast with the LDA calculations orbitals contribute to the wave functions of the lowest bands and the hybridization via orbitals responsible for is “switched on” for these bands. Note that the resulting features of the band structures shown in Figure 32 are obtained from full LDA+ calculations independent of the tight-binding model and hence prove the correctness of our tight-binding model in this respect.
(a)
(b)
Another important consequence of the strong hopping across the rung is that the orbital can hybridize via with the unoccupied orbital of the ion from the same rung and the latter give a substantial contribution to the wave functions of the occupied bands. This partial delocalization of states can lead to appearance of relatively long-range terms in a TB model describing the effective hopping in the case of the CO structure with one ion per rung. The degree of the delocalization depends on the relative energy positions of the and states which can be rather sensitive to the changes of the V-O distances in the VO5 pyramid caused by charge ordering. As a result of the hybridization the spin magnetic moment, defined as an integral of the electron spin density over the atomic sphere surrounding the ion, is smaller than the value of 1 expected for spin 1/2 and is equal to ≈0.9 for both zig-zag and in-line CO models. However, together with the moment of about 0.1 inside the sphere, this gives the total magnetic moment of 1 per rung. Just as for the TB model this smearing of the magnetic moment over the rung can affect the parameters of the effective model for exchange interactions between spins in the CO phase of .
The total energies obtained from the LDA+ calculations for the CO models with different kinds of magnetic order are summarized in Table 8. The lowest total energy is calculated for the zig-zag CO model with AF alignment of moments along the chains and F interchain ordering (, Figure 30(b)), the energy of the same model but with AF inter-chain ordering () being only 2 meV higher. The difference between the lowest energies of the considered CO models is found to be 15.5 meV. Comparison of the total energies of the models with different types of magnetic order indicates clearly that AF intra-chain magnetic order is preferable for both in-line and zig-zag CO models. Calculations were also performed for some other models for CO possible in the super-cell, but their total energies were found to be much higher than those of the zig-zag and in-line models. For example, an interchange of and at every second ladder in the in-line CO model leads to double chains along direction. This increases the total energy by 125 meV. Another possible type of CO is a structure with one or two rungs doubly occupied by ions. It was found, however, that formation of the doubly occupied rung results in the energy loss of about 100 meV.
The conclusion derived from the LDA+ calculations that the zig-zag CO model (Figure 30(b)) is more favorable than the in-line one is supported by recent experimental data on the temperature dependence of the dielectric constant in [247, 248]. The observation of step-like anomalies at suggests that the low-temperature structure is of antiferroelectric type which is consistent with the zig-zag CO model. The in-line CO model, on the other hand, corresponds to the ferroelectric ordering with the spontaneous electric polarization along -axis in which case a peak in the temperature dependence of the dielectric function should be observed.
4.2.4. Effective Exchange Constants
Effective exchange constants between spins are necessary input values for theoretical models aimed at the description of magnetic excitations in . In [245] they were estimated by mapping the LDA+ total energies onto the mean-field energy of a localized Heisenberg model. Assuming that the total energy differences between the configurations with the same CO but different orientations of magnetic moments are due to the change of the magnetic energy written as a sum of pair interactions of the Heisenberg form, one can express the exchange constants in terms of the total energy differences. The corresponding expressions for the exchange parameters introduced for the zig-zag and in-line () CO models (Figure 30) are where all the energies are given per formula unit, the upper index specifies the CO model, whereas the first and the second letters in the subscript denote the kind of the intra- and inter-chain magnetic ordering, respectively. Here we assume additionally that the absolute value of spin is equal to and remains constant. Similar expressions can be written for and exchange parameters.
The effective exchange coupling parameters calculated from the LDA+ total energies are given in Table 9. It was found that the most important parameters are meV and meV responsible for the exchange coupling along the in-line and zig-zag chains, respectively. While the exchange coupling along the in-line chains is provided by the superexchange via orbitals, the mechanism for is less obvious. It can be explained by the effective hopping of orbitals via and 2 paths taking into account the large values of the corresponding hopping terms and obtained from the TB fit to the LDA results. The important point here is that, in contrast to the LDA results, in the case of the CO phase with inequivalent V ions at the ends of a rung, the orbital contributes to the wave functions of occupied bands. An additional contribution to can appear as a result of the above-mentioned partial delocalization of the orbital over the rung due to its hybridization with the orbital of the ion. Then, these delocalized orbitals of adjacent rungs can hybridize via orbitals which gives an additional channel for the interaction between spins.
The calculated exchange constants are smaller than the value of 560 K (48.3 meV) estimated from the high-temperature magnetic susceptibility using the formulas for spin- chain [223]. However, the present calculations were performed for the case of nearly complete charge-ordering, and it is difficult to compare the results with those obtained for the high-temperature phase with the average oxidation state of V ions being . Another possible reason for the discrepancy is that the on-site Coulomb repulsion derived from the super-cell calculations may be overestimated leading to underestimated values of the exchange parameters. Indeed, and calculated with eV are about 60 meV which is already larger than the experimental value.
An important consequence of the fact that the intra-chain exchange coupling for both CO models is of comparable strength is that the experimentally observed strong dispersion of magnetic excitations in Γ-Y direction can be explained not only in the case of the in-line CO model but also within the CO model with the zig-zag ordering of ions.
The inter-chain coupling is determined by ferromagnetic effective exchange constants meV for the in-line CO model and meV and meV for the zig-zag one. This surprisingly large value of questions the applicability of the model of weakly coupled AF zig-zag chains. However, at least for small deviations from the ground state with AF intra-chain ordering, the energy gain from ferromagnetic alignment of the moments coupled by is almost exactly compensated by the energy loss due to antiparallel alignment of the moments coupled with . As a result of this compensation the total energies and of two configurations with different alignment of the nearest moments differ by 2 meV only.
The effective hopping between orbitals of the nearest V ions is much smaller than the hopping along the ladders, and it can hardly account for the large ferromagnetic . The dominant mechanism responsible for this interaction is the almost 90-degree exchange caused by the hybridization of orbital via states to unoccupied and orbitals with the same spin projection of the ion from the adjacent ladder. As the latter states are split by ≈1 eV by the on-site exchange coupling the energy gain from this hopping depends on the relative orientation of the magnetic moments and reaches its maximal value when the moments are ferromagnetically aligned. To verify that this mechanism is the most important one, we have determined from test calculations with the on-site exchange interaction switched off which was achieved by averaging the LSDA exchange-correlation potential for majority- and minority-spin electrons. calculated in this way was found to be ten times smaller in absolute value and of opposite sign which confirms that it is really governed by the on-site exchange. On the other hand, calculated in the same manner does not change so drastically as it is determined mainly by the on-site Coulomb repulsion .
As the ions coupled with and occupy equivalent crystallographic positions, one can suppose that the values of these exchange parameters should be close to each other and their difference can be used to check the numerical accuracy of the total energy calculations. Indeed, the calculated values of and differ only slightly which confirms that the calculations were performed with sufficient accuracy.
This relatively strong exchange coupling, considering the large distance between the corresponding ions, is caused by the partial redistribution of a spin between orbitals of and ions from the same rung. The mechanism responsible for and is similar to that for with the important difference that for the former the hybridization path between and unoccupied orbitals is longer and includes additionally and states which leads to a significant decrease of compared to .
4.2.5. Optical Conductivity
Authors of [249] studied the electronic structure and optical properties of the ladder compound by a joint experimental and theoretical approach. The momentum-dependent loss function was measured using electron energy-loss spectroscopy in transmission. The optical conductivity derived from the loss function by a Kramers-Kronig analysis agrees well with our results from LDA+ band structure calculations applying an antiferromagnetic alignment of the V electrons along the legs and an on-site Coulomb interaction between 2 and 3 eV. The decomposition of the calculated optical conductivity into contributions from transitions between selected energy regions of the DOS reveals the origin of the observed anisotropy of the optical conductivity.
In comparison with with a similar network of linked VO5 pyramids, the Na atom provides an additional electron to the valence band of . Since in the bands, formed by the O states, are completely filled and the energetically lowest lying unoccupied bands are formed by the V states [249], the additional electron in - occupies the rather localized V states, which determine to a great extent the unique properties of the compound. Due to the localized nature of the V electrons, the Coulomb correlations between them are rather strong and, as a consequence, conventional LSDA calculations fail to describe properly the electronic structure of . In the unit cell corresponding to the centrosymmetric structure of the high-temperature phase, a nonmagnetic metallic solution is obtained in contradiction with the experimental data. If an antiferromagnetic (AFM) order of V magnetic moments along the direction is allowed by an appropriate doubling of the unit cell, an energy gap opens in the LSDA band structure. However, the value of the energy gap is strongly underestimated. Besides, there is no experimental evidence for the existence of AFM order in .
An efficient way to take into account the strong correlations in the V shell is to use the LDA+ approach. However, this method is usually applied to ordered compounds and an additional assumption should be made in order to study the electronic structure and the optical properties of the high-temperature phase of . Since, according to the experimental data, there is no charge ordering above and all V sites are equivalent, we have assumed that the effective one electron potential at each V site is the same and equal to the average of the LDA+ potentials for and ions. In other words, the orbital-dependent potential is calculated using the occupation numbers averaged formally over the and orbital occupation numbers. Applying , the partially occupied V orbitals are the most affected orbitals. The average occupation of the majority-spin orbitals is close to 0.5, and their energy position remains unchanged as compared to LDA, whereas the unoccupied minority-spin orbitals are shifted upwards by . As a result, an insulating behavior with the magnetic moment of 0.5 per V atom or 1 per rung is immediately obtained which is independent of the kind of magnetic order along the axis. One can say that the on-site Coulomb repulsion effectively suppresses the occupation of the orbitals with the opposite spin at each rung.
The effect of the absence of a long-range AFM order in the high-temperature phase of on the electronic structure and optical properties was modeled by performing calculations for spin waves defined by a vector with varying from 0.5, corresponding to AFM order of V magnetic moments along the direction, to 0 at which all V magnetic moments are ferromagnetically aligned. In these calculations all were set to be zero whereas the were chosen in such a way that the V ions situated at the same rung had the same magnetization direction. It has been found that the relative orientation of the magnetization at V sites of neighboring ladders, which is also determined by , has only minor effect on the calculated band structure.
The calculations were iterated to self-consistency for and then one iteration was performed for spin waves with other values of [249]. The comparison of the band energies confirmed that the ground state of the system is antiferromagnetic in accordance with previous estimates for the exchange coupling constants between V spins in the direction.
The densities of the V and O states, calculated for eV and AFM order of V magnetic moments along the direction are shown in Figure 33 [249]. In Figure 33(b) the density of the V states calculated for (dashed lines) are also shown. Here and in the following we assume that the magnetic moments of the V ions situated at the same rung are ferromagnetically ordered. The states in the energy range from −6.5 to −2 eV are formed mainly by the O states (Figure 33(a)) with a bonding hybridization with the V states. The V states dominate in the 1.8–3 eV range, while the states with V and V characters are shifted to higher energies due to the comparatively strong hybridization with O states and form the upper part ( eV) of the conduction band, shown in Figure 33(b). The main differences in the structure of the DOS as compared to are caused by the additional electrons occupying the V bands which are empty in the case of . Since the change in the occupation of the V states is the main source of the differences between the optical spectra and other physical properties of these compounds, in the following we will focus our attention on the states originating from the V orbitals. The narrow peak in the majority-spin V DOS just below the Fermi level (Figure 33(b)) originates from that combination of the orbitals of the two V atoms on the same rung, which is orthogonal to the orbital of the atom in the center of the rung. The corresponding antibonding V – states are responsible for the DOS peak at 1 eV. In terms of the effective V–V hopping these two peaks result from the bonding and antibonding combination of the V 3 states, respectively, and the energy separation between them is determined by eV acting across the rung. Here, for the effective V–V hopping terms we use the values obtained from a tight binding fit to the LDA band structure calculated with the LMTO method. The minority spin states of bonding character are shifted to higher energy by the effective Coulomb repulsion and lie above the antibonding peak. While the energy of the latter is governed by and thus does not depend on , the relative position of the minority-spin states depends on the exact value of . Finally, the peak at ~2.5 eV arising from the antibonding states is almost lost in the contributions from the other states of the conduction band, mainly formed by the remaining V states hybridized with O states.
It should be noted that for both spin directions the width of the bonding peaks is much smaller than 0.7 eV, obtained from LDA calculations, because the relatively strong hybridization along the direction governed by eV is suppressed due to the AFM order. However, as , which defines the magnetic structure along the direction, decreases, the width of the peaks increases and reaches the LDA value when V magnetic moments are ordered ferromagnetically. As for the antibonding states, the dispersion of the corresponding bands along the Γ-Y direction is much weaker already in LDA and the width of their DOS does not depend on .
In Figure 34 the optical conductivity derived by means of a Kramers-Kronig analysis from the EELS spectra with small momentum transfers ( Å), aligned parallel to the crystallographic and directions (Figures 34(a) and 34(b)), is shown together with the and spectra, calculated for using the LSDA () and LDA+ with and 3 eV (Figures 34(c) and 34(d)) [249]. Comparing the spectra (Figures 34(a) and 34(c)) one can see that for this polarization the theoretical spectra are weakly affected by and already the LSDA curve agrees well with the experimental one. The calculated position of the low-energy peak in centered at 1 eV does not depend on and coincides almost perfectly with the position of the corresponding experimental maximum. However, the calculations overestimate the magnitude of the peak and fail to reproduce its asymmetric shape. The peak corresponding to the experimental feature at 3.4 eV lies at slightly lower energy in the LSDA calculations and shifts upwards to ~3.7 eV with increasing .
For (Figures 34(b) and 34(d)) the situation is quite different. In this case the LSDA calculations result in the optical gap of 0.2 eV which is significantly smaller than the experimental value. In contrast with the position of the low-energy peak is sensitive to and becomes close to the experimental value for eV. A less strong but still noticeable dependence on can be found in the energy range between 2.5 and 4 eV. Comparing the theoretical spectra calculated with different values of to the experimental ones, one can conclude that the best overall agreement between the theory and the experiment is achieved for lying in the range between 2 and 3 eV.
The observed correspondence between the calculated and the experimental spectra allows us to draw additional information from the detailed analysis of the theoretical spectra. In order to understand better the origins of the features of the optical conductivity and the reasons for their different dependence on the value of , we analyzed the contributions to the optical conductivity originating from the interband transitions between the initial and final states which are formed by the V states. In Figure 35 the results of the decomposition of ((a) and (c)) and ((b) and (d)) calculated with eV are presented. The grey areas in Figures 35(a) and 35(b) show the contributions of the transitions from the occupied V bands. In Figures 35(c) and 35(d) the transitions with the final states restricted to the antibonding V and the bonding V states are denoted by light grey and grey areas, respectively. The hatched areas show the contributions from interband transitions to higher-lying V states. The full and spectra are drawn by a solid line without shading, respectively.
Comparing the shaded areas in (a), (b) and (c), (d) of Figure 35, one can see that the peaks below 2 eV in both, and spectra, are formed by transitions with the initial states given by the occupied V bands (Figures 35(a) and 35(b)). However, due to different selection rules for the dipole optical transitions the final states for these transitions are quite different for both polarizations. The final states for transitions responsible for the 1 eV peak in are antibonding V bands (Figure 35(c)). As it was mentioned above, the bonding-antibonding splitting of states is determined by the hybridization within a rung and is not affected by . When the momentum transfer is parallel to the direction the matrix elements for these transitions are zero, whereas the transitions into the unoccupied bonding bands become active (Figure 35(d)). The position of the latter is sensitive to the strength of the on-site Coulomb interaction which explains the strong dependence of the position of the low-energy peak in on the value of . In a “many-body language” the transition can be interpreted as excitations leading to the appearance of doubly occupied rungs.
In order to avoid misunderstanding we have to note here that due to the AFM order along the direction the states with both spins projections contribute to the Bloch wave functions and the bands are labeled as majority and minority spin only for convenience according to the dominating contribution of the states of a chosen V site. In view of this remark the term “ transition” does not imply that the transition occurs between the states with opposite spins, which would become possible if the relativistic effects were taken into account, but simply specifies the initial and final bands involved in the transition.
Concerning the energy range between 3 and 4 eV, Figures 35(c) and 35(d) illustrate that for both polarizations the spectral features are determined by transitions from the top of the part of the valence band formed mainly by the O states. The peak in at 3.7 eV is due to transitions into the bands. The initial and final states for these transitions are of the same character as for those which determine the shape of the spectra of just above the absorption threshold. The transitions into the antibonding states are completely suppressed for this polarization, while for they play an important role in the formation of the shoulder in this energy range, whereas the contribution of the O → V transitions are less pronounced. It is striking that these theoretical results explain the double-peak structure in which is also visible in our experimental data (see Figure 34(b)) but is not resolved in the spectra from optical measurements that we referred to, previously. Finally, the transitions from the occupied bands to the part of the conduction band originating from the V states give rise to the nonvanishing intensity of the calculated spectra in the range between the peaks (1.5–3 eV), also observed in the experiment (see Figure 34).
As mentioned above, the magnitude and the strongly asymmetric shape of the low-energy peak are not reproduced by the calculations (see Figure 34) for both crystallographic directions. The discrepancies are the result of two possible sources: firstly, an oversimplified treatment of the charge fluctuations in the high-temperature phase by using an averaged one-electron potential and secondly the possibly not justified assumption that the V magnetic moments are antiferromagnetically aligned along the direction. A more rigorous consideration of the charge disorder in the V sublattice of is beyond the capabilities of the LDA+ approach in its present formulation and thus will be studied in more detail by applying cluster calculations described in the next section. However, the influence of the deviations from the long-range AFM order on the optical spectra can be estimated by performing the calculations for spin waves.
The optical conductivity spectra calculated for different values of are shown in Figure 36. Since the change of the magnetic structure affects most strongly the bands formed by the V states of bonding character (see Figure 33), the spectral features originated from the transitions in which these bands are involved demonstrate the strong dependence on . The change of the shape and the intensity of the peak at 1 eV in (Figure 36(a)) is the most noticeable. As increases, the peak becomes less intensive and its maximum shifts to higher energy. Since the final states for the corresponding transitions, that is, the antibonding V states, remain very narrow independently of the magnetic order along the direction, the widening of the peak reflects the change of the density of the occupied V states. The shape of the low-energy peak in (Figure 36(b)) does not change with increasing , but its intensity rapidly decreases and vanishes completely for when the V magnetic moments order ferromagnetically. The drop of intensity is explained by the decrease of the weight of the majority-spin states in the final-state wave functions. For the initial and final states are formed by pure majority- and minority-spin states, respectively, and the corresponding transitions are forbidden since the relativistic effects were not included in the calculations. The spectral features in the energy range between 3 and 4 eV are also influenced by an increase of , but the changes are less pronounced. The comparison of the spectra for the spin-spiral structures (Figure 36) with the experiment (Figures 34(a) and 34(b)) shows that the accounting for deviations from the AFM order improves the agreement between the theoretical and experimental magnitude of the low-energy peaks of and . However, the asymmetric shape of the peaks is not reproduced by the calculations.
For some values of the optical conductivity was calculated for different relative orientations of the magnetization at neighboring ladders (not shown). The changes of the spectra were found to be very small which can be explained by the smallness of the eV hopping term which couples the V ions belonging to the consecutive ladders.
4.2.6. Summary
The extended TB model based on explicit V–O hopping which describes the dispersion of the four bands formed by V states has been constructed by fitting the parameters to the band structure of calculated using the LMTO method [245]. Taking into account the hopping terms between oxygen orbitals allows to reproduce the suppressed dispersion of the upper pair of V derived bands. The O –O hybridization is especially important in the case of the CO phases as it affects the dispersion of the occupied bands and leads to an important additional hopping term in an effective vanadium only tight-binding model, which has not been considered previously.
From the results of LDA+ calculations performed for different models for the CO phase of , it has been found that the energy of the CO model with zig-zag ordering of ions is lower than the energy of the in-line CO model. Relatively strong dispersion of bands is observed for both CO models when moments are ordered ferromagnetically along the corresponding chains.
Effective exchange constants between magnetic moments were determined from the comparison of the LDA+ total energies calculated for different kinds of MO within the zig-zag and in-line CO models [245]. It was found that for both CO models the strongest exchange interaction is the AF intra-chain coupling, whereas the coupling between the moments of the nearest ions in the case of the zig-zag CO model was found to be ferromagnetic. The calculated exchange constants are compatible with the experimental values determined from the high-temperature susceptibility. The calculated intra-chain exchange coupling for both in-line and zig-zag CO models is of comparable strength. The important consequence is that the experimentally observed strong dispersion of magnetic excitations in Γ-Y direction can be explained not only in the case of the in-line CO but also within the CO model with the zig-zag ordering of ions.
The LSDA+ calculations quite well represent the energy positions in the optical conductivity using the on-site Coulomb interaction eV and an antiferromagnetic ordering of the electrons along the ladders. The anisotropic behavior of the optical conductivity could be explained by the different characters of the underlying optical transitions. While the transitions between 0.5 and 1.7 eV from the highest occupied band mainly composed by the bonding combination of V states into the lowest unoccupied band of antibonding V – states occur on the same rung in the direction, in the direction they can be considered as a hopping process to one of the adjacent rungs. The features of above 3 eV could be assigned to excitations of the O electrons.
5. Ce Compounds
In recent years cerium monopnictides (CeAs, CeSb, and CeBi) and monochalcogenides (CeS, CeSe, and CeTe) attract a great attention partly due to the discovery of the three largest ever measured Kerr rotation angles of 90°, , and for cleaved single crystals of CeSb, CeS, and CeBi, respectively [250]. Cerium monopnictides and monochalcogenides crystallize in simple rock-salt structure, and each ion caries a single electron. Furthermore, the cerium monochalcogenides are metals with approximately one conduction electron per formula units, as was confirmed from Hall effect measurements [251], while cerium monopnictides are well-compensated semimetals with a low concentration of conduction electrons and valence holes in the band [252]. The temperature dependence of the electrical resistivity of the cerium monochalcogenides exhibit Kondo behavior [253], indicating nonnegligible mixing. Furthermore, the Ce monochalcogenides order magnetically at low-temperature in the antiferromagnetic fcc type-II structure [254]. The ordered magnetic moments are rather small and equal to 0.31, 0.45, and 0.66 for SeS, CeSe, and CeTe, respectively. The Ce monopnictides have magnetic moments of 0.57, 2.06, and 2.10 for CeAs, CeSb, and CeBi, respectively.
5.1. CeS, CeSe, and CeTe
The optical and polar Kerr spectra of Ce monochalcogenides were measured by Reim [255] and Pittini et al. [256, 257]. All three Ce chalcogenides exhibit sharply peaked Kerr rotations and ellipticities at the energies of their plasma minima. The largest Kerr rotation was observed for CeS, for which was reported by Pittini et al. [257]. Smaller peak rotations up to were observed for CeSe and CeTe.
Theoretical investigations of the optical and MO of some of the Ce monochalcogenides were carried out by Lim et al. [258], Cooper et al. [259], Yaresko et al. [62], Price et al. [260], and Antonov et al. [261].
Figure 37 shows the energy band structure of CeS for three independent fully relativistic spin-polarized band structure calculations treated the electrons as: (a) itinerant electrons using the local spin-density approximation; (b) fully localized, putting them in the core; and (c) partly localized using the LSDA+ approximation. The energy band structure of CeS with the electrons in the core can be subdivided into three regions separated by energy gaps. The bands in the lowest region around −13 to −14.5 eV (not shown in Figure 37) have mostly S character with some amount of Ce character mixed in. The next six energy bands are S bands separated from the bands by indirect energy gap. The highest region can be characterized as Ce spin-split bands. The sharp peaks in the DOS at the Fermi energy and at around 2 eV above are due to and states, respectively (see Figure 37). There is a single energy band crossing the Fermi level.
(a)
(b)
(c)
The LSDA+ band structure calculations [261] started from a configuration for the ion with one on-site energy shifted downward by /2 and 13 levels shifted upwards by this amount. The energies of occupied and unoccupied levels are separated by approximately . However, the states are not completely localized, but may hybridize, and together with all other states their energy positions relax to self-consistency. The LSDA+ energy bands and total DOS of CeS [261] for eV are shown in Figure 37. For ions one band is fully occupied and situated between S and Ce states, but the other thirteen bands are well above the Fermi level hybridizing with Ce states.
Figure 38 shows the calculated imaginary part of the energy-loss function , absorptive diagonal part of the optical conductivity , and the optical reflectivity compared with experimental data [257]. The calculated spectra have been convoluted with a Lorentzian whose width is 0.2 eV to approximate a lifetime broadening.
The predominant structure of CeS as well as CeSe and CeTe reflectivity spectra is the edge near 3 eV [257]. This sudden drop is characteristic for metallic rare-earth chalcogenides and is due to a plasma oscillation interfering with interband excitations. This plasma resonance causes the golden color for all metallic rare-earth sulfides. The energy of the conduction electron plasma resonance in the presence of the interband excitations is given by . In the particular case of CeS this condition is fulfilled at eV for the LSDA+ calculations, and the maximum peak of the energy-loss spectrum in Figure 38 is shifted only very little from this energy as a result of damping. The correct energy position of the plasma edge in CeS can be obtained only by taking into account interband transitions. The calculations treating electrons as core electrons place the zero crossing energy of at higher energies (at 3.2 eV) in comparison with the LSDA+ calculations, hence gives a wrong energy position for the major minimum in the optical reflectivity spectrum (Figure 38). On the other hand, the calculations with the electrons in core produce more sharp conduction electron plasma resonance than the LSDA+ calculations (Figure 38). As a result, the former calculations give better agreement with the experiment in the absolute value of the minimum of the reflectivity spectrum.
The best agreement between theory and the experiment for the optical reflectivity was found to be when we used the LSDA+ approximation (Figure 38). The Coulomb repulsion strongly influences the electronic structure and the optical spectra of CeS. Due to removing the states from the Fermi level, the diagonal part of the optical conductivity in the energy interval of 0 to 3.5 eV has only small infrared peak (see Figure 38). This peak originates from interband transitions between eigenvalue surfaces that are quasiparallel around the Γ symmetry point. These quasiparallel bands are visible along Γ-L and Γ-K symmetry directions (see Figure 37). The very broad double-peak structure observed between 4 and 10 eV is due to transitions from bands with predominantly S character to unoccupied Ce and bands, respectively.
The calculation of the optical conductivity where the ’s are treated as band states reproduces two additional structures in the 0.0 to 3.5 eV energy interval, namely, the peaks at 0.9 and 2.0 eV (Figure 38). Both of the peaks involve the interband transitions. The second peak is responsible for the deep minimum in the optical reflectivity at 1.8 eV which is not observed in the experiment [257] (Figure 38).
After consideration of the band structure and optical properties we, turn to the magneto-optical spectra. The polar magneto-optical Kerr effect was measured on CeS, CeSe, and CeTe in [257]. All three spectra are quantitatively very similar. They are dominated by a sharp and large negative Kerr rotation peak of , , and detected at photon energies of 3.04, 2.60, and 1.99 eV for CeS, CeSe, and CeTe, respectively, with a remarkably small width of 0.1 eV [257]. These Kerr rotation peaks are significant, in particular if one considers the small magnetic moment achieved in the sample at the condition of the experiment. Particularly meaningful is the Kerr rotation peak of observed in CeS [257] with a magnetic moment of only 0.31 /Ce. This extraordinary peak corresponds to the highest ever observed specific Kerr rotation of / and to the second largest ever measured Kerr rotation after the record of 90° recently detected on CeSb [262]. In Figure 39 we show the experimental [257] and MO Kerr spectra of CeS, as well as the spectra calculated with LSDA and LSDA+ approximations. This picture clearly demonstrates that the better description is unambiguously given by the LSDA+ approach. The LSDA spectra have extra peaks at 0 to 1 eV which is caused by extra structure present in the interband dielectric tensor. Responsible are interband transitions involving the hybridized states, which in the LSDA approach exhibit a maximum resonance near . In the LSDA+ approach, the state energies are shifted due to the on-site Coulomb interaction . As a result, the transitions involving the states do not take place at small photon energies any more, and the structures at 0 to 1 eV disappear from Kerr spectra. The calculations in which the electrons are treated as quasicore (not shown) are able to reproduce a very similar structure as the LSDA+ calculations, but, due to the lack of corresponding interband transitions, the off-diagonal part of the optical conductivity is nearly zero, so that a very small Kerr rotation is obtained. Although the LSDA+ calculations made much better work in the comparison with LSDA one, they still produce the less-sharp plasma resonance and hence give smaller rotation angle of than experimentally observed .
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In Figure 40 we show the experimental [257] and LSDA+ results for Kerr spectra of CeSe and CeTe. The results of the LSDA approach are not shown here, but we mention that these do by far not reproduce the experimental data as good as LSDA+ approaches [62]. The main peak in the Kerr rotation spectra in Figure 40 is not found to be due to optical transitions stemming directly from the nearly localized level. Instead, these peaks are due to a plasma minimum in the denominator and nonzero .
5.2. CeSb and CeBi
The optical and MO properties of CeSb were investigated by Schoenes and Reim [263] and Reim et al. [264], whereas its optical conductivity to 20 eV was measured by Kwon et al. [265]. Reim et al. [264] observed the onset of a large Kerr rotation that reached −14° at 0.5 eV, but that energy was the lower end of the spectral range they could measure. Pittini et al. [262] extended the low-energy limit to 0.23 eV and observed a record Kerr rotation which increased to reach −90° at 0.46 eV, and then jumped to +90° at the same energy, and decreased with increasing photon energy. Note that the reflectivity of CeSb at the maximum of Kerr rotation was found to be 28% [262]. 90° is the absolute maximum value that can be measured. It is two orders of magnitude larger than the values that are commonly measured for transition-metal compounds and about one order of magnitude larger than values maximally achieved for other lanthanide and actinide compounds [46]. Later on Salghetti-Drioli et al. [266] prepared well-characterized single crystals of CeSb but could not reproduce the record Kerr rotation on these crystals. Instead only a peak of −17° at 0.46 eV was observed. They remeasure the CeSb specimen on which record Kerr rotation was found and obtained for this sample the 90° rotation. Salghetti-Drioli et al. polished the surface of the sample on which Pittini had measured the record rotation, in order to exclude surface oxidation effects, but after the surface treatment only a small Kerr rotation could be measured from the sample [266]. Salghetti-Drioli et al. suggest that the observed 90° Kerr rotation might not be the intrinsic rotation of CeSb but could be caused by a surface oxide layer.
The discovery of 90° Kerr rotation in CeSb attracts a great interest from theorists. Several groups tried to produce the Kerr rotation spectrum from the first principles or analyze theoretically the possibility of attaining a 90° Kerr rotation. Using the exact equation for the polar Kerr rotation Uspenskii et al. [267] pointed out that a 90° rotation can occur only when the absorptive parts of the diagonal and off-diagonal permittivities are zero. The absolute maximum value of Kerr rotation can be achieved at energy with zero reflectivity, and it is also attainable for the reflectivity of the order of 30–50% and hence the observation of 90° rotation in principle be possible in CeSb with its 28% reflectivity at 0.46 eV. Pustogowa et al. [268] also examined the possibility of a 90° rotation using the modeled MO conductivity and reflectivity with a singular oscillator strength and the SO coupling as a parameter. She was able to obtain a 90° rotation for various values of the SO parameter.
To investigate the nature of a record polar Kerr rotation in CeSb several first-principle calculations of the diagonal and off-diagonal optical conductivity and polar Kerr effect of CeSb were carried out in [62, 258–260, 269, 270].
The energy band structure of CeSb in the LSDA and LSDA+ approaches is presented in Figure 41 from [62, 270]. The LSDA calculations place the DOS at and just above the Fermi level. The Coulomb repulsion strongly influences the electronic structure of CeSb. For ions thirteen unoccupied states are situated at 2 to 4 eV above the Fermi level hybridizing with Ce states. A single occupied state is located at −3.2 eV in good agreement with photoemission measurements which detected the level slightly deeper than −3 eV [271–273]. The LSDA+ calculations also improve the magnetic moments producing spin and orbital magnetic moment equal to −1.012 and 2.960 , which yield a total moment of 1.948 . The experimental value obtained for the antiferromagnetic ground state is equal to [274, 275]. The LSDA strongly underestimates the magnetic moments producing spin, orbital, and total magnetic moments equal to −0.897, 1.511, and 0.614, respectively [270].
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Liechtenstein et al. [269] and Yaresko et al. [62] show that LSDA+ calculations also give a substantial improvement over LSDA result in diagonal and off-diagonal optical conductivity of CeSb.
The complex polar Kerr spectra of CeSb were evaluated by Yaresko et al. [62] and Antonov et al. [270]. The maximal Kerr angle calculated with the LSDA approach was relatively large, about −12° to −22° depending on value of life-time broadening. The LSDA+ approach produces a relatively larger polar Kerr angle. The results for the Kerr spectra of CeSb from [62] are shown in Figure 42(a). A giant Kerr rotation of 60° is less than the observed value of 90°. Pittini et al. [262] observed that the maximum Kerr rotation depends on the magnetization and that therefore the intrinsic quantum state plays an important role. In addition, the record Kerr effect occurs close to a plasma minimum. Both observations agree with what was found in the calculations (Figure 42). The denominator nearly vanishes due to the particular frequency dependence of . A small denominator is in itself not sufficient for obtaining a large Kerr rotation. Also , which relates to the magnetic polarization, is important. The level in CeSb is a completely spin and orbitally polarized state, which has a large magnetic moment of about 2 . The level is, however, located 3.2 eV beneath , and therefore it cannot contribute directly to the peak rotation. It was found that the level plays nevertheless a crucial role, because, due to hybridization of valence states with the anisotropically polarized state, the valence bands become anisotropically polarized. This anisotropic polarization leads to an asymmetrical coupling of the left- and right-hand circularly polarized light at small photon energies. The asymmetrical light coupling leads in turn to a relatively large , which causes the huge Kerr rotation. To emphasize the importance of the anisotropic hybridization, it was performed also quasicore calculations for the level [62]. One was obtained a very similar , but due to the lack of anisotropic hybridization, becomes nearly zero. Consequently, only a very small Kerr rotation is obtained in quasicore calculations (not shown). We should note that the large angle of −60° represents the maximal Kerr rotation that could be achieved in the LSDA+ calculations. In this case no lifetime broadening was included and the plasma frequency was slightly changed. The first-principles LSDA+ calculations give smaller but still substantial Kerr angle of −45° [62]. We also should mention that the theoretical Kerr spectrum is more narrow and shifts toward smaller energies in comparison with the experiment.
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Figure 42(a) shows the results for the Kerr spectra of CeSb calculated in LSDA approximation [270] in comparison with latest experimental data obtained by Salghetti-Drioli et al. [266] on well-characterized single crystals of CeSb. The theoretical spectrum is convoluted on lifetime effect using the parameter of 0.1 eV. Surprisingly LSDA theory produces the experimental spectrum rather good in the shape, position, and amplitude.
The MO Kerr spectra of CeBi has also a considerable interest. In most compounds the magnitude of the Kerr effect is proportional to the spin-orbit (SO) coupling interaction. The MO Kerr effect in MnBi is, for example, larger than that in MnSb, because the SO coupling on Bi is larger than that on Sb. One could thus expect that the Kerr angle in CeBi should be as large as, or even larger than, that of CeSb. However, this is not found to be the case [257].
In Figure 43 we show the experimental [257] and theoretical Kerr spectrum of CeBi [276]. The measured maximal Kerr rotation amounts only to −9°. The LSDA+ approach (with eV) explains the measured MO Kerr spectrum of CeBi fairly well. There is a small energy difference of 0.1 eV in the position of the rotation maximum, and the calculated Kerr ellipticity deviates above 0.5 eV from the experimental curve.
The fact that the Kerr rotation of CeBi is far less than that of CeSb is fully reproduced by the calculations [62, 276], but it is not consistent with our experience that the Kerr effect is proportional to the magnitude of SO coupling. The imaginary part of is for CeBi as large as that of CeSb, but if we compare the of CeBi to that of CeSb, then we find that the denominator does not become as small for CeBi. The resulting Kerr angle of CeBi is therefore not as large as that of CeSb.
5.3. CeFe2
Among the Ce–T series the C15 Laves phase compounds, CeT2 (T = Ni, Co, Fe), which stand out as archetype of the –Ce class, have been studied intensively [277].
CeFe2 compound presents a strong anomaly in physical properties in comparison with other compounds, which originates from hybridization. Firstly, there is a strong reduction in the lattice parameter in comparison with the expected smooth decrease through the series, leading to a lattice constant for CeFe2 as small as that for HoFe2. Secondly, the magnetic properties present characteristic features. The Curie temperature ( K) is depressed by a factor of nearly 3 as compared to LuFe2 ( K, La−Fe compounds do not exist). The magnetic moments are also anomalously low (, , coupled antiferromagnetically to each other). The saturation magnetization is equal to 2.30 /f.u., the magnetic susceptibility follows the Curie-Weiss law with an effective moment of 7.4 /f.u. [278]. Moreover, magnetic and neutron-diffraction studies have shown that the substitution of small amount (only a few %) of Fe by Co, Al, Si, or Ru reveals a second magnetic transition with an abrupt loss of ferromagnetism at Neel temperature , lower than the bulk-ordering temperature . In particular, with Co substitution an antiferromagnetic phase appears for K [279]. From recent neutron scattering experiments for CeFe2, Paolasini et al. reported that there is an AFM spin fluctuation with a propagation vector below about 100 K even in the FM state [280]. They also revealed that the AFM spin fluctuation with the same vector exists in the FM state for , and that it changes into a typical AFM spin wave in the AFM state at low temperatures [281]. The AFM spin fluctuation and the AFM spin wave observed by them are associated with the Fe spins. They also showed that the AFM state of is not a simple collinear AFM structure but a noncollinear one. From magnetization measurements using a CeFe2 single crystal, Fukuda et al. revealed that the magnetization along the direction at 5 K is anisotropically suppressed by applying hydrostatic pressure [282]. According to their conclusion, such anisotropic suppression of the magnetization originates from the anisotropic Ce hybridizations with the strong magnetoelastic effect. Fujiwara et al. [283] carried out the magnetization measurements of single-crystal CeFe2 under hydrostatic pressures up to 8 kbar and show that the magnetization is quite anisotropically suppressed at 5 K even in the cubic symmetry by applying the hydrostatic pressure, while the neutron diffraction studies indicate that the antiferromagnetic spin fluctuation with a propagation vector is enhanced by applying hydrostatic pressure of 15 kbar.
All anomalous physical properties of CeFe2 suggest that the Ce states in CeFe2 hybridize strongly with the other valence electrons, notably the Fe valence states [277].
The band structure investigations of the CeFe2 were carried out by several authors [284–287]. Already first band structure calculation by Eriksson et al. [284] using the LMTO method within atom sphere approximation (ASA) shows that total magnetic moments at the Fe and Ce sites are aligned antiferromagnetically. It was an indication on itinerant character of the states in CeFe2. The relativistic effects was found to be relatively small. Trygg et al. [286] provided the energy band structure calculations of CeFe2 including spin-orbit coupling and orbital polarization using the full potential linear muffin-tin orbital (FP-LMTO) method. Later on Konishi et al. [287] obtained similar results using also the FP-LMTO. The Ce electrons were treated as itinerant band electrons. They also reported on results from high-energy spectroscopic measurements using core-level and valence-band photoemission, inverse photoemission, and soft X-ray absorption techniques. It was found that the Ce partial density of states obtained from the band structure calculations agree well with the experimental spectra concerning both the peak position and the bandwidth, if the surface effects are properly taken into account. Combined analysis of the experimental and theoretical results indicate very strong hybridization of the Ce states with the delocalized band states, mainly the Fe states.
In [288], authors focus their attention on the theoretical investigation of the X-ray magnetic circular dichroism in CeFe2 compound. Actually XMCD is one of the most promising techniques to reveal local electronic and magnetic properties in a variety of magnetic materials, essentially because of its element as well as shell selectivities. In fact, with the help of circular polarized X-rays of good quality, arising from third-generation synchrotron facilities, a lot of data have been accumulated up to now on XAS and XMCD of transition-metal and rare-earth compounds [6, 289, 290].
The first experimental XMCD measurements of CeFe2 at the Ce absorption edges were carried out by Schillé et al. [291]. The uncertainty of these experiments was too large to allow a reliable quantitative determination of the absolute value of the local moments on Ce. Later, using high-quality sample and better experimental conditions, Delobbe et al. [292] measured the X-ray magnetic circular dichroism at the Fe , Ce , and Ce absorption edges of CeFe2. Application of the sum rules yields both the magnitude and the direction of the magnetic contributions to the total moment in CeFe2. A total Ce magnetic contribution of −0.29 (, ) and a ratio for the contribution were found, which confirmed that the states are highly hybridized in CeFe2. The experimental results of XAS and XMCD spectra for CeFe2 at the Ce and Fe absorption edges were presented in [279, 291]. Mizumaki et al. [293] measured Ce XMCD spectra in compounds for , and . Klose with coworkers investigated magnetic circular dichroism on Ce/Fe multilayers at the Fe and Ce absorption edges [294].
As for the XMCD and photoemission spectroscopy (PES) studies of compounds, it is widely believed that the spectra are well described by the single-impurity Anderson model (SIAM) [295, 296]. Indeed during many years Kotani’s group demonstrates remarkable agreement between theoretically calculated and the experimentally measured XMCD spectra in the rare-earth compounds with different degree of the localization using the SIAM approximation [297–301]. To describe the hybridization of states with spin-polarized transition metal states of surrounding ions, they used a cluster model. The method contains several adjustable parameters (such as the energy of the level, , Coulomb interaction between the electrons, , and between and states, , core hole potentials and , and hybridization parameter between and conducting states ). By proper choice of these parameters they were able to describe quite well the shape of the XMCD spectra at the edges for the considered series of , including CeFe2 compound (see review paper [302]). Recently, however, it has been argued that for systems, in which the Ce states hybridize strongly with the other valence electrons, calculations based on the density-functional theory (DFT) may give an equally good or even better description of the PES and XMCD spectra than the SIAM analysis [6, 287, 303]. However, one should bear in mind that calculations based on DFT are not strictly applicable for excited state properties, in contrast to the ground-state properties, such as the magnetic moments of the ground state, which are typically the focus of these calculations. Nevertheless, the electronic structure obtained from such calculations is often compared with photoemission or XMCD data, and good agreement between experiment and calculations is frequently observed. In the limit of complete screening of the excited state, one would expect ground-state density-functional calculations to be able to describe the spectra well. Still there are only a few ab initio calculations of the XMCD spectra in rare-earth compounds [304–308] and no such calculations for the CeFe2 compound in literature as far as we know.
CeFe2 crystallizes in the cubic structure (space group no. 227) and belongs to the large class of C15 Laves-phase compounds. The unit cell consists of two formula units (i.e., six atoms) with a lattice constant Å [309], Ce ions occupy the Wyckoff positions (, , ). Fe ions occupy the positions (, , ). The Ce atoms have twelve Fe atoms as nearest neighbors (at 3.0265 Å distance), while for Fe there are six Fe atoms (at 2.581 Å distance) and six Ce atoms (at 3.0265 Å distance).
5.3.1. Energy Band Structure
The fully relativistic spin-polarized total and partial density of states (DOSs) of cubic ferromagnetic CeFe2 are presented in Figure 44 for the LSDA approximation. The results agree well with previous band structure calculations [284, 286, 287].
There is a visible Ce –Fe as well as Ce –Ce hybridization at 0 to 2 eV above the Fermi level. The Ce empty states possess two major peaks at around 3 eV and 7 eV above the Fermi level. As we will see later these two peaks are responsible for the double structure of the Ce XAS at the edges.
A large magnetic moment at the Fe site induces spin splitting of the itinerant Ce and Ce states through exchange and hybridization effect. From our LSDA calculations, it has been deduced that the total moment /f.u. (experimental saturation magnetization is 2.30 [287]) is the result of the antiparallel coupling between Fe moment (1.473 ) and cerium moment (−0.693 ). The total Ce moment corresponds to a contribution of −0.275 and a contribution of −0.221 . The orbital Ce moment was calculated to be 0.151 . The spin and orbital Fe moments are 1.502 and 0.064 , respectively.
The LSDA calculations show an unusual antiparallel magnetic coupling between and transition metal moments. The first experimental evidence of an ordered Ce moment in CeFe2 antiferromagnetically aligned with respect to the Fe moments was obtained from powder neutron diffraction experiments [310]. Few years later, a combination of polarized and unpolarized neutron diffraction measurements on a CeFe2 single crystal [311] confirmed the previous results obtained on powder samples. The partial magnetic moments in CeFe2 have been studied also using Compton scattering [312] and X-ray magnetic circular dichroism [292]. In all experiments, an antiparallel coupling of the Ce and Fe moments is found. This coupling is also reproduced in band structure calculation [284, 286–288]. The antiparallel coupling of the moments is a strong indication that the Ce states in CeFe2 are delocalized. Indeed, in CeFe2 Fe and Ce states strongly hybridize to form bonding and antibonding bands. When a moment develops at the Fe sites the energy of spin-up states is lowered, reducing the hybridization for the spin-up states. The opposite effect occurs for the spin-down states, and the induced Ce spin moment is therefore antiparallel to the Fe spin moment [284]. The hybridization between the Fe and Ce states is more pronounced in the minority channel (see Figure 44). When a Ce electron is localized, the direction of the spin moment is dictated by the polarization of the electrons so that the Ce and Fe spin moments are always antiparallel. In a ion with the configuration, the spin moment is accompanied by an orbital moment which is larger than the spin moment and, according to Hund’s third rule, is antiparallel to it. Hence, for the localized electrons, the coupling of the total Ce and Fe moments is ferromagnetic. When the Ce orbital moment is quenched due to band formation, the coupling becomes antiparallel. It should be mentioned that the band structure calculations for CeFe2 [288] show that the Ce spin moment is partially induced by the direct Ce –Fe hybridization, which is an additional argument in favor of the delocalized character of the Ce electrons.
Figure 45 shows the comparison of the experimental photoemission spectrum with the partial DOS calculated by the LSDA and LSDA+ approximations. The LSDA approach better represents the energy position of the occupied part of Ce bands. The principal question is the energy position of the empty states, which is usually answered by optical or X-ray bremsstrahlung isochromat spectroscopy (BIS) measurements. BIS spectrum is consisted from two major peaks. The first peak situated at around 1 eV above Fermi energy is derived from Ce empty bands. From analysis of Figure 45 we can conclude that the LSDA calculations place the empty bands in better agreement with the experiment than the LSDA+ approach.
5.3.2. Ce XMCD Spectra
For various ferromagnetic Ce intermetallic compounds, X-ray absorption spectra and their X-ray magnetic circular dichroism have been extensively studied for Ce edges [302]. According to experimental observations, both XAS and XMCD spectra for strongly mixed-valence Ce compounds, which also include CeFe2 exhibit a double-peak structure. According to the atomic-like consideration the two peaks in the XAS are associated with a mixed-valence state in CeFe2: in the presence of the hole at the core level the lower energy peak corresponds to the configuration and the higher energy peak to the configuration. One should mention, however, that Ce states in CeFe2 having definitely band character extend at more than 15 eV (see Figure 44). Therefore, one would expect that the calculations based on density-functional theory may give an equally good or even better description of the XAS and XMCD spectra at the edge than the atomic-like SIAM analysis.
The XMCD spectra at the Ce edges are mostly determined by the strength of the spin-orbit (SO) coupling of the initial Ce core states and spin-polarization of the final empty states, while the exchange splitting of the Ce core states as well as the SO coupling of the valence states are of minor importance for the XMCD at the Ce edges of CeFe2. A qualitative explanation of the XMCD spectra shape can be provided by the analysis of the corresponding selection rules, orbital character, and occupation numbers of individual orbitals (see detailed analysis in [307]).
The LSDA approximation reasonably well describes the shape of the XAS and XMCD spectra at the Ce edges (Figure 46); however, it slightly overestimates the first low energy peak and underestimates the intensity of the dichroic signal between two positive peaks of the XMCD spectrum.
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5.3.3. Summary
The Ce electrons in the CeFe2 hybridize strongly with the Fe electrons. A large magnetic moment at the Fe site induces spin splitting of the itinerant Ce and Ce states through exchange and hybridization effect. From our LSDA calculations, it has been deduced that the total moment is the result of the antiparallel coupling between Fe moment and cerium moment. This conclusion agrees well with the neutron diffraction, Compton scattering, and X-ray magnetic circular dichroism experiments.
The theoretically calculated X-ray absorption spectra at the Ce edges have a rather simple line shape composed of two white line peaks with additional fine structures at the high-energy part of the spectra which can be assigned to multiplet structures. The dichroism at the Ce edges is very large due to strong spin orbit coupling of the initial Ce core states and large spin polarization of the final empty states.
The XAS and XMCD spectra at the Ce edge reflect the energy distribution and the orbital character of the Ce band-like states. The LSDA calculations show good agreement in the shape of the X-ray absorption spectra at the Ce edges with the experimental measurements and reproduce the observed two-peak structure of the Ce XMCD spectra.
6. Sm Monochalcogenides and Borides
6.1. Sm Monochalcogenides
The Sm monochalcogenides offer the interesting possibility to study the transition from semiconductor to the mixed-valence state as a function of pressure. First, it is of great importance to characterize the semiconducting state.
The energy band structure of SmS presented in Figure 47 with the electrons in the core can be subdivided into three regions separated by energy gaps. The bands in the lowest region around −11 eV have mostly S character with some amount of Sm character mixed in. The next six energy bands are S bands separated from the bands by an energy gap of about 7 eV. The width of the S band is about 3.2 eV. The unoccupied electronic states can be characterized as Sm bands. The sharp peaks in the DOS calculated in the LSDA just below and above the Fermi energy are due to and states, respectively (Figure 47).
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The LSDA+ band structure calculations [313] have been started from a configuration for the ion with six on-site levels shifted downward by and eight levels shifted upward by this amount. The energies of occupied and unoccupied levels are separated by approximately . The LSDA+ energy bands and total density of states of SmS for eV are shown in Figure 47. The Coulomb repulsion strongly influences the electronic structure of SmS. For ions six bands are fully occupied and situated in the gap between S and Sm states, while the hole levels are completely unoccupied and well above the Fermi level hybridized with Sm states which results in a nonmagnetic ground state with the Sm ion in the divalent state. The theoretically calculated energy gap eV which is formed between Sm and Sm states is in good agreement with the experimentally estimated 0.15 eV derived from the activation energy [5].
The LSDA+ energy bands and total density of states of SmSe and SmTe for eV are shown in Figure 48. Their electronic structures are very similar to the SmS one with six Sm bands fully occupied and the hole bands completely unoccupied and well above the Fermi level hybridized with Sm states. Theory gives energy gaps between Sm and bands equal to 0.47 and 0.67 eV in SmSe and SmTe, respectively. The corresponding experimental values are equal to 0.45 and 0.65 eV [5].
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Photoemission experiments, both X-ray (XPS) and ultraviolet (UPS), have been of central importance for understanding mixed-valence materials. The partial DOS of the occupied part of the SmS calculated in LSDA and LSDA+ approximations is compared with XPS measurements [314] in Figure 49. The theoretically calculated DOS cannot, of course, fully account for the multiplet splitting. Therefore, Figure 49 presents the DOSs taking into account the multiplet structure of the final-state. This multiplet structure consists of 3 terms , , and [314]. In Figure 49 the XPS spectrum is modeled by a weighted sum of three DOS curves. We aligned the centroid of the calculated occupied DOS peak with the centroid of the atomic final state multiplet. Although LSDA calculations produce almost the same picture as LSDA+ calculations in the case of SmS, for SmSe and SmTe the LSDA calculations place the energy bands too close to the Fermi level which leads to disagreement with measured XPS spectra (Figure 49).
In Figure 50 we show the experimental [315] real and imaginary parts of the dielectric function, and , the optical reflectivity and optical conductivity spectra, as well as the spectra calculated with LSDA, LSDA+, and the electrons in the core. This picture clearly demonstrates that the better description is unambiguously given by the LSDA+ approach. As was mentioned above, the LSDA theory produces a metallic solution and, therefore, gives the wrong asymptotic behavior for the optical reflectivity and the dispersive part of the dielectric function as . The most prominent discrepancy in the LSDA spectra is the extra peaks between 0 and 1.5 eV in the , , and optical conductivity caused by interband transitions involving the occupied and unoccupied hybridized states. In the LSDA+ approach, the empty state energies are shifted upward due to the on-site Coulomb interaction . As a result, the transitions involving the unoccupied states do not take place at small photon energies, and the erroneous peak structures around 0 to 1.5 eV disappear from the optical spectra.
The calculations in which the electrons are treated as quasicore are able to reproduce correct asymptotic behavior for the optical reflectivity and the dispersive part of the dielectric function as similar to the LSDA+ calculations, but it fails in producing a peak at around 0.6 eV in the absorptive part of the dielectric function and optical conductivity spectra. This peak is mostly determined by the interband transitions.
6.2. High-Pressure Golden Phase of SmS
The history of the Sm monochalcogenides as MV materials started at the beginning of the 1970s when Jayaraman et al. [316] and then Bucher et al. [317] discovered a pressure-induced semiconductor-metal transition and suggested that the metallic state would be mixed valent. It was a surprise that SmS showed this transition occurring at the incredibly low pressure of 6.5 kbar. Starting the pressure above the phase transition and decreasing, a large hysteresis is observed and the MV state snaps back to a semiconductor state at 1.5 kbar. For SmSe and SmTe the pressure-induced valence transition is continuous and is completed at higher pressures, about 45 and 60 kbar, respectively [5].
By increasing external pressure and hence, decreasing the lattice constant, the widths of Sm and bands are increased. In addition, the crystal-field splitting of the states in SmS is also increased. At a given pressure the band overlaps with the states and the energy gap becomes zero (Figure 51). It happens at a lattice constant around 5.70 Å [5]. Starting from the overlap of and states, electrons will spill into the band leaving a state behind. The ionic radius of is about 15% less than the radius of , so that simultaneously with more electrons in the conduction band the lattice will shrink, thus further increasing the crystal-field splitting of the states, resulting in an avalanche effect and a first-order valence transition. However, the valence transition does not go all the way to trivalency but stops where the gain in electronic energy is compensated by an increase in lattice strain energy [5].
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The LSDA+ energy bands and total density of states of SmS for are shown in Figure 51. There are five bands fully occupied and hybridized with the bottom of the S states. The unoccupied states are well above the Fermi level. The initially empty 6th hole level became partly occupied and pinned at the Fermi level in the process of self-consistent relaxation with occupation number equal to 0.25 (valence 2.75+). It is a typical situation for mixed-valent crystals.
We can use two different representations in the construction of the LSDA+ method, namely, and representations. Most of rare earths and their compounds have a rather large spin magnetic moment; therefore, it is natural to use the representation in the calculations of their electronic structure. In this case one chooses the projection of the orbital momentum onto the spin direction for the occupied states. The SmS black phase as well as SmSe and SmTe have a nonmagnetic ground state; therefore, it was used in that case the representation [313]. For fully occupied states the projections of the total moment were equal to , and .
The situation is not clear for golden SmS. It was used both of the representations for the calculation of the electronic structure of the golden high-pressure phase of SmS in [313]. Figure 51 presents the energy band structure of golden SmS in the representation with for the hole state. Due to the existence of a hole in the shell, the LSDA+ gives a so-called low magnetic moment ground state with total magnetic moment equal to 0.240 (spin and orbital moments have opposite directions with values equal to −0.305 and 0.545 , resp.). The representation gives a high-spin magnetic moment ground state in SmS with total magnetic moment equal to 4.636 at each site (spin and orbital moments have opposite directions with values equal to 5.501 and −0.865 , resp.). We should mention, however, that, although the LSDA+ band structure calculations give always a nonzero samarium magnetic moment, in golden SmS all the efforts to find a magnetic superstructure in high-pressure SmS using neutron experiments have remained unsuccessful. However, one cannot exclude either a weak magnetic component below the limit of the experimental sensitivity (samples for high-pressure measurements are very tiny) or an incommensurate structure giving peaks at positions not searched in the neutron experiments. The evaluation of the magnetic ground state of golden SmS from first principles requires further investigation.
The pinning of a partly occupied 6th level strongly depends on the lattice constant. The increasing of the valency with decreasing of the lattice constant which was found in the band structure calculations [313] can be considered as qualitative theoretical support of the conclusion derived from various experimental measurements [5] that the application of pressure enhances the state relative to state in SmS. The theoretically calculated samarium valency was found to be equal to and for high- and low-spin solutions, respectively. The experimentally estimated one is about from spectroscopic methods and susceptibility measurements [318–320] and about from Vegard’s law analysis of lattice constant measurements [320].
Some experimental results indicate that the golden phase of SmS could be a narrow-gap semiconductor. Evidence for a gap comes from the activation behavior of the electrical resistivity and point contact measurements [5]. The estimations from the point-contact spectra shows a possible gap of about 6.4 meV [5]. On the other hand, some experiments indicate that there may not be a gap but rather a pseudogap, and the hybridization does not occur over whole Brillouin zone. Although the temperature dependence of the resistivity in the golden phase of SmS is semiconductor-like, the resistivity is increased only one order of magnitude with cooling from room temperature to several ’s, whereas, for example, in SmB6 it is 5 orders of magnitude [5]. Direct optical measurements of mechanically polished (high-pressure golden phase) SmS by Travaglini and Wachter [321] show that, in contrast to SmB6, the reflectivity does not tend to a constant value for , but it seems to rise toward 100% as for a metal. Besides, there is a linear with term in the specific heat presumably due to conduction electrons [322]. The LSDA+ band structure calculations of golden SmS [313] produce a pseudo gap at the Fermi level with a peak just above and a shoulder below the Fermi level with predominantly character. It should be mentioned that, when the density of states at is small compared to the giant density of states of the peaks, the resistivity may nevertheless appear activated over a certain temperature range as experimentally observed, but for the lowest temperatures metallic conductivity should persist [321].
6.3. SmB6
SmB6 is classical mixed-valence narrow gap semiconductors. This class of materials is characterized by their electronic properties, which at high temperatures are associated with a set of independent localized () moments interacting with a sea of conduction electrons, while at low temperature the electronic properties resemble those of a narrow gap semiconductor. SmB6 is the first compound in which the phenomena of MV was detected directly by X-ray absorption [323]. Despite more than 35 years of experimental and theoretical efforts, many fundamental aspects of the microscopic description of the MV ground state and the nature of valence fluctuations are still under discussion [5, 324, 325]. The main problem is the origin of the MV ground state, which seems intimately connected with the gap formation. One question is whether Kondo insulating materials actually are true insulators at low temperatures or whether an intrinsic small conduction-electron carrier concentration is present [326]. Infrared absorption [327, 328], inelastic neutron scattering [329–332], optical conductivity [333], electron tunneling [334], and electrical transport [335–337] measurements all detect a small electronic gap meV. However, the low-temperature transport properties of SmB6 are manifestly metallic, having a large but finite resistivity below ~4 K [335–337]. There is considerable controversy whether these in-gap states are intrinsic and present in pristine SmB6 [329–332, 338, 339], or extrinsic and dictated entirely by sample quality [335–337, 340, 341]. The size of the energy gap determined by different methods varies considerably. For example, the value of the gap in SmB6 is equal to 2.7 meV by tunneling spectroscopy [334], 5 meV from the temperature dependence of the electrical resistivity [335–337], and 16 meV by point-contact spectroscopy [342]. Direct measurements of the low-temperature dynamical conductivity and dielectric permittivity of single crystalline SmB6 give evidence for a 19 meV energy gap and an additional narrow donor-type band lying only 3 meV below the bottom of the upper conduction band [343].
The average valence of Sm in the hexaboride was established to be 2.56 at room temperature and to vary slightly with temperature by measurements of X-ray absorption [323, 344], lattice constant [345], X-ray photoemission [346], and the Mössbauer isomer shift [347].
The energy band structures of SmB6 have been calculated by Yanase and Harima [348] in the local spin density approximation and in [349] using the LSDA+ approximation.
The compound SmB6 has the CaB6 type crystal structure with space group (no. 221) and lattice constant equal to 4.1333 Å. The structure of samarium hexaboride may be viewed as a CsCl-type lattice with the cesium replaced by samarium and the chlorine by a B6 octahedron. Figure 52 shows the energy band structure of SmB6 calculated within the LSDA and the LSDA+ approximations [349]. The energy band structure of SmB6 with the LSDA approximation can be subdivided into three regions separated by energy gaps. The bands in the lowest region around −14 to −16 eV (not shown) have mostly B character with some amount of Sm character mixed in. The next group of energy bands are B bands separated from the bands by an energy gap of about 3 eV. The width of the B band is about 8.8 eV. The Sm bands are partly occupied. They are also separated from B states by the energy gap of around 0.7 eV. The sharp peaks in the DOS calculated in the LSDA just below and above the Fermi energy are due to and states, respectively (Figure 52). They cross the Sm bands and hybridize with them. There is a small direct energy gap at the Fermi level of around 23 meV.
(a)
(b)
(c)
The LSDA+ energy bands and total DOS of SmB6 for eV are shown in Figure 52. The Coulomb repulsion strongly influences the electronic structure of SmB6. For ions five bands are fully occupied and hybridized with the B states. The unoccupied states are above the Fermi level at around 1 eV. A single level is fully unoccupied and situated at about 0.34 eV above the Fermi level.
The LSDA+ band structure calculations [349] have been started from a configuration for the ion with six on-site energies shifted downward by and eight levels shifted upward by this amount. The energies of occupied and unoccupied levels are separated by approximately (Figure 52). For ions eight hole levels are completely unoccupied and well above the Fermi level and hybridized with Sm states. The bands are situated in close vicinity of the Fermi level. They cross the bottom of Sm band. Figure 53 shows an expanded view of the LSDA+ energy band structure and total DOS for SmB6 with ions. There is a hybridization gap at the Fermi level meV. Although the LSDA+ calculations [349] used a starting configuration with fully occupied bands, in the process of self-consistent relaxation, one of the doubly degenerate bands becomes partly unoccupied and situated above the Fermi level around the X symmetry point (Figure 53) due to Sm hybridization. There is a small peak in the DOS above the Fermi level at around 0.03 eV with predominantly character. This peak contains 0.02 holes. In other words, the LSDA+ calculations produce a semiconducting ground state in SmB6 with noninteger Sm valency equal to .
The XPS spectra for SmB6 indicate multiplet structure which can be identified with both and configurations being present. Figure 54 shows the SmB6 XPS spectrum [346] in comparison with the occupied part of the partial LSDA+ DOS calculated with a multiplet structure of the final states taken into account in the same way as for SmS in previous section. Figure 54 shows the final-state multiplet structure presented in [346]. (4 final state) has the multiplets , , and. ( final state) has the multiplets , , , and [346]. It is clear that the structures between 0.0 and −5.5 eV binding energy should be assigned to the final-state multiplet structure derived from six fully occupied bands (), and the structures between −5.5 and −13 eV are associated with the final-state multiplet structure of the ions. The agreement with the positions of the multiplet peaks indicates that the LSDA+ is giving reasonably correct average positions for the occupied states.
Let us turn now to the optical properties of SmB6. Experimental investigation of the reflectivity spectra of SmB6 was performed by Kierzek-Pecold [350] in a narrow energy range from 1 to 5.6 eV. After that, Travaglini and Wachter measured the reflectivity spectrum of SmB6 in the energy range from 1 meV to 12 eV at 300 K and 4 K for investigation of the energy gap [333]. Kimura with coworkers measured the optical spectra of all single-crystal rare-earth hexaborides (, Ce, Pr, Nd, Sm, Eu, Gd, Th, Dy, Ho, Yb, and Y) in the energy region from 1 meV to 40 eV at 300 K and 13 K [328, 351–353].
Figure 55 shows with a logarithmic scale the calculated optical conductivity spectra of SmB6 compared with experimental data measured at 13 K [328]. Calculations were performed for both the divalent and trivalent phases of SmB6. The experimentally measured optical conductivity spectrum has two strong peaks at 0.12 and 0.5 eV and a steep rise at 3 eV (Figure 55). As might be expected the experimental optical conductivity spectrum contains key features of both the divalent and trivalent theoretically calculated spectra. However, the three major peaks have different origins in the divalent and trivalent phases. A steep increase of optical conductivity starting at around 3 eV is mostly determined by B → Sm interband transitions around the X symmetry point in the divalent samarium compound. The same feature in the trivalent phase can be described as a combination of the B → Sm and Sm → Sm interband transitions. These transitions also occur mostly around the X symmetry point (Figure 52). The low-energy peak at 0.12 eV in the divalent phase can be explained as interband transitions between occupied Sm mixed states and unoccupied Sm states near the X symmetry point. The same structure in the trivalent Sm phase is due to interband transitions among hybridized Sm bands along Γ-X, Γ-M, X-M, and X-R symmetry directions. This peak is shifted at around 0.1 eV toward smaller energies in comparison with the experimental measurements. The peak at 0.5 eV in the divalent phase arises from interband transitions between occupied Sm mixed states and unoccupied Sm states near the X symmetry point and Γ-X and X-M symmetry directions. The same structure in the trivalent samarium phase is due to interband transitions between occupied Sm states and the empty 6th hole band along Γ-X, Γ-M, and X-M symmetry directions.
As we mentioned above, the XPS measurements cannot distinguish between an inhomogeneously mixed or a homogeneously mixed compound, that is, whether and ions are integer valent and statically mixed or the charge between them just fluctuates slower than the time resolution of XPS. The experimental optical conductivity spectrum also can be considered as a mixture of both the divalent and trivalent spectra. From other experiments, SmB6 is known to be a homogeneous mixed-valence semiconductor compound with a small energy gap [5]. Mössbauer isomer shift versus temperature measurements for SmB6 by Cohen et al. clearly shows that above 700 K and down to 4.2 K the degree of valence mixing is a constant of around 2.56 [347]. The LSDA+ band structure calculations [349] produce a metallic state with trivalent samarium ions if we start the self-consistent procedure from . On the other hand, if we used as starting configuration with fully occupied levels (), we will able to produce a correct semiconductor ground state for SmB6 with a small hybridization energy gap and a theoretically calculated valency . A comprehensive theory for the MV state is needed to provide a quantitative measure of the mixing between the two configurational states. The LSDA+ calculations are only able to provide specific details for the individual configurational states.
6.4. YbB12
The compound YbB12 has the UB12 type crystal structure with space group (no. 225) and lattice constant equal to 7.464 Å. The crystal structure of YbB12 can be understood as NaCl type with the sodium replaced by ytterbium and the chlorine by 12 B atoms.
The band structure calculations in [349] have been performed using three independent fully relativistic spin-polarized calculations. The electrons have been considered as (1) itinerant electrons using the local spin-density approximation (2) fully localized, putting them in the core, and (3) partly localized using the LSDA+ approximation. Figure 56 shows the energy band structure of YbB12 for all three approximations. The energy band structure of YbB12 with electrons in core can be subdivided into three regions. The bands in the lowest region around −15.5 to −10 eV have mostly B character with some amount of Yb character mixed in. The next group of the energy bands are B bands separated from the bands by a small energy gap of about 0.4 eV. The width of the B band is about 8 eV. The Yb bands are partly occupied and cross the Fermi energy. They slightly overlap with B states. The sharp peaks in the DOS calculated in the LSDA just below the Fermi energy are due to Yb and states (Figure 56). They cross Yb bands and hybridize with them. There is a small direct energy gap of about 65 meV at the Fermi level.
(a)
(b)
(c)
(d)
The LSDA+ energy bands and total density of states of YbB12 for eV are shown in Figure 56. For divalent Yb ions all 14 bands are fully occupied and situated closely below the bottom of Yb band. They are split due to spin-orbit coupling by eV. There is a small hybridization gap at the Fermi level. In other words, the calculations indicate a nonmagnetic semiconducting ground state in YbB12 for Yb atoms in the divalent state. The theoretically calculated energy gap meV is formed between Yb and Yb states. The experimentally estimated energy gap is about 10 meV from the activation energy [355–357], 25 meV from optical measurements [358], and 200–300 meV from tunneling experiments [359].
For the trivalent Yb ion, thirteen electron bands are well below the Fermi energy and hybridized with the B states (Figure 56). The 14th unoccupied hole level is above the Fermi level at around 1.5 eV. It should be mentioned that such an electronic structure is appropriate for the development of the Kondo scenario.
The partial DOS of the occupied part of YbB12 calculated in the LSDA+ approximation is compared with ultraviolet photoelectron spectra (UPS) [354, 360] in Figure 57 [349]. The experimental spectra were measured using both single-crystalline [354] and polycrystalline [360] samples. The double-peak structure at 0.1 and 1.5 eV binding energy reflects the spin-orbit doublet of the density of states. The corresponding spin-orbit doublet for the DOS is situated at −6.0 and −7.6 eV (Figure 57(a)).
Theoretically calculated DOS cannot, of course, fully account for the multiplet splitting. Therefore, we present in Figure 57(b) the DOSs taking into account the multiplet structure in the same way as for SmB6. We used the theoretical final-state multiplet structure presented in [361]. has the configuration . The state has one hole in shell and cannot reproduce the experimentally measured four-peak structure in the XPS. One would expect only the spin-orbit doublet, and the 4-peak structure is almost certainly due to surface effects.
After consideration of the band structure and UPS spectra of YbB12, we turn to the optical spectra. Optical reflectivity experiments have been conducted by Okamura et al. on single crystals of YbB12 [358]. They found that upon cooling below 70 K, a strong suppression of the optical conductivity was seen in the far-infrared region, reflecting the opening of an energy gap of ~25 meV. A narrow, asymmetric peak was observed at ~40 meV in , which was attributed to optical transitions between the Yb -derived states across the gap [358]. They also measured the optical spectra of single crystalline LuB12 as a reference material.
Figure 58 shows with a logarithmic scale the calculated optical reflectivity and diagonal part of optical conductivity spectra of LuB12 compared with the experimental data [358]. To incorporate the intraband contribution to the optical conductivity tensor, the phenomenological Drude model [362] with intraband Drude relaxation time eV was used. A sharp onset is seen in the LuB12 reflectivity spectrum near 1.6 eV, which can be identified as the plasma edge () due to a metallic response of free carriers. The peak structures above are due to interband transitions between electronic states far apart from . Figure 58 clearly shows the important role of intraband transitions in formation of the optical conductivity spectrum in LuB12.
Figure 59 shows the calculated optical reflectivity spectra of YbB12 compared with experimental data measured at 290 K [358]. Calculations were performed for both the divalent and trivalent phases of YbB12. The intraband optical transitions in Drude form with inverse intraband Drude relaxation time eV also included. The optical reflectivity spectrum of YbB12 measured at 290 K has a metallic character, very similar to with the same plasma edge at 1.6 eV. The two spectra are almost identical for the energy interval above . Below , in contrast, the spectra are strictly different for the two compounds. In LuB12, is nearly flat and shows a sharp rise, which is typical of a good metal, while in YbB12 there is a broad dip in giving rise to a prominent peak at 0.25 eV in . As can be seen from Figure 59 a broad dip in comes from YbB12 with divalent Yb ions. Our LSDA+ calculations produce the reflectivity spectrum in YbB12 with trivalent ytterbium ions very similar to the LuB12 spectrum. The experimentally measured optical reflectivity spectrum of YbB12 can be considered as a mixture of two spectra coming from di- and trivalent ytterbium ions. Good agreement between theory and experiment can be reached if one uses the sum of the optical reflectivity spectrum consisting of 20% ytterbium divalent and 80% ytterbium trivalent spectra (Figure 59).
The experimental investigations of the temperature dependence of the optical spectra of YbB12 presented in [358] show that, as the temperature is lowered from 290 K to 78 K, there is no drastic change in the optical conductivity spectrum. The IR peak becomes slightly enhanced and blue-shifted. At 78 K the spectra are still metallic. However, at 20 K the spectral weight below ~40 meV in is strongly depleted and the spectrum becomes typical of a semiconductor with an energy gap of around 25 meV. The reflectivity spectrum at 20 K is also typical of a semiconductor having the asymptotic value at of 0.83. The gap development coincides with the rapid decrease of the magnetic susceptibility in exactly the same temperature range [358].
Figure 60 shows the calculated diagonal part of optical conductivity spectra of YbB12 [349] compared with experimental data [358]. Calculations were performed for both the divalent and trivalent phases of YbB12. The experimentally measured optical conductivity spectrum in the 0 to 0.6 eV energy interval has two peaks at 0.05 and 0.25 eV (Figure 60). The experimental optical conductivity spectrum of YbB12 contains key features of both the divalent and trivalent theoretically calculated spectra. The low-energy peak at 0.05 eV in the optical conductivity spectrum originates from trivalent phase and can be explained as interband transitions between occupied and unoccupied Sm states along Γ-X and X-W symmetry directions (Figure 56). The prominent peak in spectrum at around 0.4 eV (the corresponding experimental peak situated at 0.25 eV) is mostly derived from the interband transitions between occupied Yb bands and empty Yb bands of divalent phase in the vicinity of the W symmetry point as well as along the X–W symmetry direction (Figure 56). The theoretically calculated spectrum in divalent phase is shifted toward higher energies due to the larger theoretically calculated energy gap (65 meV) in comparison with the experimental one (25 meV).
6.4.1. Summary
The Sm monochalcogenides SmS, SmSe, and SmTe constitute a very interesting system exhibiting behavior due to strongly correlated electrons. While the standard LSDA approach is unable to correctly describe the electronic structure of these materials because of the strong on-site Coulomb repulsion, , the LSDA+ approach is remarkably accurate in providing detailed agreement with experiment for a number of properties.
In contrast to LSDA, where the stable solution for Sm monochalcogenides at ambient pressure is metallic, the LSDA+ method gave an insulator with energy gaps of 0.15, 0.45, and 0.65 eV (the experimental gaps are 0.18, 0.47, and 0.67 eV) for SmS, SmSe, and SmTe, respectively. The Coulomb repulsion strongly influences the electronic structure of Sm monochalcogenides. For ions six bands are fully occupied and situated in the gap between chalcogen and Sm states. The hole levels are completely unoccupied and well above the Fermi level hybridized with Sm states. The LSDA+ theory predicts that the samarium ion in these compounds is in an integer divalent state. It also shows a gradual decrease of the energy gap with reduction of the lattice constant. The LSDA+ theoretical calculations describe well the optical spectra of Sm monochalcogenides.
When applying external pressure to SmS and, hence, decreasing its lattice constant, the widths of Sm and bands are increased and the crystal-field splitting of the states is also increased. At a given pressure the band overlaps with the states. This leads to a first-order valence phase transition. The gap in SmS is closed at Å in good agreement with experimental measurements of SmS transport properties under pressure. For SmS with ions five bands are fully occupied and hybridize with chalcogenide states. The initially empty hole 6th level in the process of self-consistent relaxation becomes partly occupied with the DOS maximum situated in close vicinity of the Fermi level in the golden phase of SmS. The occupation number of the 6th hole level is equal to 0.45 (valence ) in a good agreement with the experimental estimates from spectroscopic methods and susceptibility measurements.
In conclusion we would like to point out that, while the LSDA+ approach does a very good job in the treatment of correlation effects in SmS, SmSe, and SmTe at normal pressure, it is still unclear how well it performs in describing the mixed-valence state in golden SmS in the pressure range from 6 to 20 kbar. On one hand, we found the pinning of a partly occupied 6th level at the Fermi level, which is the typical situation for mixed-valence systems. On the other hand, the LSDA+ calculations always produce a nonzero magnetic moment in the high-pressure phase of SmS, although all attempts to find any sign of magnetic ordering in this system gave no positive results for the last 30 years. It is more likely that our LSDA+ calculations describe well the situation in the metallic phase of SmS at pressure kbar with trivalent samarium ions.
We should mention that the experimental situation in golden SmS differs from that in SmB6 in the sense that in the later system a new generation of samples of much better quality became available during recent years, and more reliable data about transport properties and infrared spectroscopy were obtained. In SmS we still use old experimental data, and it is difficult to ascertain the full validity of measured gaps or pseudogaps as well as other properties based on the experiments of the early 1970s. The physical nature of the mixed-valence state in golden SmS requires further investigation theoretically as well as experimentally.
As classical mixed-valence narrow gap semiconductors SmB6 and YbB12 constitute very interesting systems exhibiting behavior due to strongly correlated electrons. The LSDA calculations provide an inadequate description of the electrons in SmB6 and YbB12 due to improper treatment of the correlation effects.
The Coulomb repulsion strongly influences the electronic structure of SmB6. For ions eight hole levels are completely unoccupied and well above the Fermi level hybridized with Sm states. The bands are situated in close vicinity of the Fermi level. One of the levels is slightly unoccupied and extends just above the Fermi level around the X symmetry point, producing a noninteger Sm valency equal to 2.02+. There is a small hybridization gap at the Fermi level meV. The theoretically calculated energy gap is larger than the experimentally estimated one of around 3.6 to 5.2 meV determined from the activation energy and optical measurements. For five bands are fully occupied and situated at around 6 eV below the Fermi level. A 6th hole level is fully unoccupied and situated at about 0.34 eV above the Fermi level. The average positions of the occupied states in and calculations are in agreement with XPS measurements.
In the LSDA+ energy band structure calculations of the electronic structure of YbB12 with divalent Yb ions all 14 bands are fully occupied and situated closely below the bottom of the Yb band. They are split due to spin-orbit coupling by eV. There is a small hybridization gap at the Fermi level. The theoretically calculated energy gap meV between Yb 4 and Yb states is somewhat larger than the gap estimated from the activation energy and optical measurements and smaller than observed in tunneling experiments. For the trivalent Yb ion, thirteen electron bands are well below the Fermi level and hybridized with the B states. They are separated from a hole state by the correlation energy . The 14th unoccupied hole level is well above the Fermi level at around 1.5 eV.
The optical spectra of YbB12 can be considered as a mixture of two spectra coming from di- and trivalent ytterbium ions. Good agreement between theory and high-temperature optical reflectivity spectrum can be reached if one uses the sum of the optical reflectivity spectrum consisting of 20% ytterbium divalent and 80% ytterbium trivalent spectra. Low temperature measurements show that below 20 K there is a gap development in the optical conductivity and reflectivity spectra of YbB12. The low energy peak at 0.05 eV in the optical conductivity spectrum originates from the trivalent phase and can be explained as interband transitions between occupied and unoccupied Sm states along Γ-X and X-W symmetry directions. The prominent peak in the spectrum at around 0.4 eV is mostly derived from interband transitions between occupied Yb bands and empty Yb bands of the divalent phase in the vicinity of the W symmetry point as well as along the X-W symmetry direction.
We should mention that the situation in YbB12 is still vague both experimentally and theoretically, and that more experimental data may help clarify the picture. If ytterbium in this compound is practically trivalent, as is claimed based on recent measurements of X-ray absorption and inelastic neutron-scattering by Alekseev et al. [363], then the gap in the tunneling and other experiments could be ascribed only to a Kondo insulator (KI) state. However, it is difficult to understand this. The necessary precondition for the KI state is a nearly half-filled single conduction band, but LSDA+ band structure calculations with ions produce several sheets of Fermi surface. The influence of the degree of valence mixing on the formation of the Kondo insulator state in YbB12 will require further theoretical and experimental investigations.
7. Tm Monochalcogenides
The Tm monochalcogenides TmS, TmSe, and TmTe constitute a well-known family of strongly correlated electron systems. They form a very interesting group of materials in which many characteristic phenomena are expressed. In the series of the Tm monochalcogenides one has the interesting possibility to go from integer trivalent metallic TmS to integral divalent semiconducting TmTe through intermediate-valence TmSe [5, 364, 365]. The unique feature of thulium compounds compared with intermediate-valence materials containing cerium, samarium, or europium is that both ground-state configurations of thulium have a nonzero magnetic moment. TmS exhibits antiferromagnetic order which is an almost type II sinusoidally modulated structure below K [366]. It has been classified as a Kondo lattice compound due to a metallic resistivity which increases Kondo-like down to about 15 K [4, 367–369]. TmSe has attracted interest because of the valence fluctuation between and configurations, Kondo effects, antiferromagnetic order, and a possible metal-insulator transition. This compound has the peculiarity that two magnetic valence states and are involved in the valence fluctuation. Evidence comes from photoemission experiments [346, 364, 365, 370–373] and also from measurements related to magnetic properties, resistivity, and specific heat [374–378]. However, the situation is so complicated that there is no overall consistent explanation of the physical properties of this compound. The resistivity of TmSe shows a Kondo-like logarithmic temperature dependence at high temperatures followed by a sharp increase at K, which is thought to be a transition into an insulating state [377, 379, 380]. This anomaly in the vicinity of shows a very complicated response to external magnetic fields and to pressure [376, 381].
TmTe is a magnetic semiconductor with a localized 13th level between a filled Te valence band and an empty Tm conduction band [365]. The lattice constant and the Curie constant show that the Tm ions are divalent at ambient pressure [364]. TmTe is interesting in its own right, especially since it was recently reported [382] to undergo a phase transition at K, far above the magnetic-ordering temperature ( K depending on the specimen). This transition was ascribed to the onset of long-range ordering among the Tm quadrupolar moments, but the exact mechanism is still controversial [383].
7.1. TmS
7.1.1. Band Structure
The theoretical study of the electronic structure, optical and magneto-optical spectra of TmX (X = S, Se, and Te) have been done in [384]. It was performed three independent fully relativistic spin-polarized band structure calculations. The electrons have been considered as (1) itinerant electrons using the local spin-density approximation, (2) fully localized, putting them in the core, and (3) partly localized using the LSDA+ approximation. An important difference with respect to treating the electrons as core electrons is that in the LSDA+ calculation all optical transitions from the states are taken into account.
Figure 61 shows the energy band structure of TmS for all three approximations. The energy band structure of TmS with the electrons in the core can be subdivided into three regions separated by energy gaps. The bands in the lowest region around −15 eV have mostly S character with some amount of Tm character mixed in. The next six energy bands are S bands separated from the bands by an energy gap of about 6.5 eV. The width of the S band is about 3.7 eV. The spin splitting of the S bands is very small (about 0.06 eV at the X symmetry point (Figure 61)). The highest region can be characterized as Tm spin-split bands. It is important that the top of the S bands is at −3.5 eV below the Fermi level since it means that all the interband transitions in the energy interval of 0.0 to 3.5 eV take part within the Tm bands (see below). The sharp peaks in the DOS calculated in the LSDA at the Fermi energy and near 2 eV below are due to 4 and 4 states, respectively (Figure 61).
(a)
(b)
(c)
The LSDA+ band structure calculations [384] have been started from a configuration for the ion with twelve on-site energies shifted downward by /2 and two levels shifted upward by this amount. The energies of occupied and unoccupied levels are separated by approximately . We emphasize, however, that the states are not completely localized, but may hybridize, and together with all other states their energy positions relax to self-consistently.
The LSDA+ energy bands and total density of states (DOSs) of TmS for eV are shown in Figure 61. The Coulomb repulsion strongly influences the electronic structure of TmS. For ions twelve bands are fully occupied and hybridize with S states. The 14th hole level is completely unoccupied and well above the Fermi level. A hole 13th level is pinned at the Fermi level. Although it was used a starting configuration with zero occupation of 14th and 13th levels, in the process of self-consistent relaxation initially empty 13th level become partly occupied due to pinning at the Fermi level with occupation number equal to 0.12 (valence ) in good agreement with the experimental estimations () by off-resonance UPS [373]. A fundamental aspect of this observation is the pinning of the 13th state at to be a robust property of the TmS compound: it happens irrespective of the precise value of .
Photoemission experiments, both X-ray (XPS) and ultraviolet (UPS), have been of central importance for understanding mixed-valence materials (see the review of the early work by Campagna et al. [346]). In rare-earth photoemission, when the photon ejects an electron from the shell it leaves behind a configuration, hence the kinetic energy distribution curve of the emitted electron measures the spectra of the final-state hole. The final-state has a characteristic multiplet splitting which serves as a fingerprint, and these are accurately resolved and calculable in rare-earth photoemission. By identification of the final-state hole the initial state can be inferred.
The partial DOS of the occupied part of the TmS calculated in LSDA and LSDA+ approximations is compared with UPS measurements [371] in Figure 62. The calculated DOS has been broadened to account for lifetime effects and for the experimental resolution. The Tm states essentially do not contribute to XPS and UPS because of the low ionization cross-section compared with that of the Tm states [385]. Hence, the measurements only indicate the excitation energies of trivalent and divalent Tm, relative to the Fermi level. The LSDA calculations places the energy band right at the Fermi level (Figure 61) producing in the DOS a double peak between 0 and −3 eV (Figure 62). In the LSDA+ calculations twelve fully occupied bands are situated between −4 and −8 eV in the DOS and a partly filled 13th band produces a small peak at around −0.5 eV binding energy (Figure 62).
The LSDA+ DOS cannot, of course, fully account for the multiplet splitting. Therefore, we present at the bottom panel in Figure 62 the LSDA+ DOS taking into account the multiplet structure of the final state. The multiplet structure consists of 15 terms, nine of which are the most intensive (, , , , , , , , and ) [346]. The relative intensities for the multiplet peaks were obtained on the basis of Cox calculations [387] who used the fractional parentage method [388]. In this method Hund’s rule ground state is assumed for electrons and then the coefficients of fractional parentage (Racah’s) for the configurations are calculated. The intensities for the various configurations (multiplets) are just the square of the coefficients of fractional parentage. In the bottom panel in Figure 62 UPS spectrum is modeled by a weighted sum of nine LSDA+ DOS curves. The centroid of the DOS has been aligned with each term of the atomic final-state multiplet and summed up the spectra scaling them according to the relative intensities of the multiplets. The agreement between theory and the UPS measurements is very good. It is clear that the structures between −4.5 and −16 eV binding energy should be assigned to the final-state multiplet structure derived from twelve fully occupied bands () and the structures between 0.0 and −4.5 eV are associated with the final-state multiplet structure of the partly occupied 13th level.
From the good agreement between theory and UPS measurements we may conclude that the LSDA+ calculations give an accurate position for the occupied bands. Figure 63 shows the experimental BIS spectrum of TmS [386] compared with the calculated energy distribution for the unoccupied partial Tm (()) and (()) density of states in the LSDA and LSDA+ approximations. The experimental spectrum consists of two maxima at about 0.9 eV and 4 eV above the Fermi level. The first narrow peak was identified as having character, whereas the second broad peak was associated with −6 states [386]. The LSDA places the empty states right at the Fermi level which contradicts the experimental data (Figure 63). The LSDA+ calculations place the maximum of the 14th hole level well above the Fermi level around 0.7 eV. The 13th hole level is partly occupied with its maximum DOS situated 0.025 eV above the Fermi level (Figure 61). Due to a rather large experimental resolution of the BIS spectra (~1 eV) [386] one experimentally observes essentially only a single BIS peak instead of two, although, a shoulder can be discerned split off from the main peak [386]. The LSDA+ calculations give the correct position of both the and states (Figure 63) within the experimental resolution.
7.1.2. Optical Spectra
More precise information on the band positions may be obtained from optical measurements. Although such measurements have much better resolution (the experimental resolution in optics is always in the meV range) in comparison with XPS and BIS, they produce complex functions containing information of both the initial and final states simultaneously (joint density of states) and are strongly influenced by the optical transition matrix elements.
Figure 64 shows the calculated real and imaginary parts of the dielectric function, and , the optical reflectivity and imaginary part of the energy-loss function Im[] compared with experimental data [389]. On the basis of the results of the LSDA+ band structure calculation, the observed optical reflectivity spectrum (Figure 64) can be sorted into the respective interband transition groups: (1) metallic high reflectivity below ~1 eV, (2) a steep edge between ~1 and ~2.5 eV, and (3) above the minimum at ~2.7 eV some less pronounced structures with a broad maximum of between 5 and 7 eV mostly caused by interband transitions.
The predominant structure of the TmS as well as TmSe reflectivity spectra is the edge at 2 eV. This sudden drop is characteristic for metallic rare-earth chalcogenides and is due to a plasma oscillation interfering with interband excitations [389]. This plasma resonance causes the golden color of TmS crystals as it does for all metallic rare-earth sulfides. The energy of the conduction electron plasma resonance in the presence of the interband excitations is given by . In the particular case of TmS this condition is fulfilled at eV, and the maximum peak of the energy-loss spectrum in Figure 64 is shifted only very little from this energy (by −0.05 eV) as a result of damping. The correct energy position of the plasma edge in TmS can be obtained only by taking into account interband transitions. The calculations treating electrons as core electrons place the zero crossing energy of at higher energies in comparison with the LSDA+ calculations and as a result give a wrong energy position for the plasma resonance (Figure 64).
To search for possible optical interband transitions, the reflectivity of a TmS single crystal has been measured between 2 meV and 12 eV at room temperature and at 6 K [386]. One should mention that the observation of an optical transitions is quite rare, especially when the metal has a large carrier concentration as in the case of TmS with about one carrier per formula unit. The large amount of carriers effectively screen the optical transition as most of the light intensity gets reflected by the plasmons. The chances to observe the optical transitions in a metal become only realistic when the energy of the optical transitions is very small since the intensity of the transition scales with [386]. Such a situation occurr in TmS where the partly occupied 13th hole level is very close to the Fermi level with its maximum DOS situated 25 meV above the Fermi level (Figure 61). Reflectivity measurements of TmS single crystals in the mid-infrared region reveal two lines near 53 and 90 meV [386]. The authors interpreted these features as optical transitions from the partly filled conduction states near the Fermi level into the empty crystal-field split 13th band states (acoustic and optical phonon modes are situated at 13 and 37 meV resp. according to Raman scattering measurements [386]). Another less pronounced feature was observed in the reflectivity spectrum measured at 6 K around 0.9 eV. The insert of Figure 64 shows the unbroadened theoretically calculated optical reflectivity in the 0 to 1 eV energy interval with two well-pronounced minima at 0.11 and 0.9 eV. These features reflect the interband transitions from occupied states to empty 13th and 14th hole levels situated at 0.025 and 0.7 eV, respectively (Figure 61). In real optical experiments such transitions are obscured by broadening from intraband Drude-like transitions, life-time effects, and to a lesser extent the experimental distortion. Figure 65 shows with a logarithmic sale the experimental optical reflectivity spectrum of TmS [386] in comparison with the theoretically calculated one.
The position of the second less-pronounced minimum that arises from the to 14th interband transitions is in good agreement with the experimental measurements (Figure 65). The crystal-field effects have not been included in the band structure calculation [384], so only a single feature in the optical reflectivity at 110 meV was obtained instead of experimentally measured two ones at 53 and 90 meV due to crystal field splitting [386]. The small shift of the theoretically calculated feature towards larger photon energies in comparison with the optical measurements may be due to a valence band electron-hole interaction in the optical spectrum which is absent in photoemission or BIS experiments as well as in our one-particle LSDA+ calculations. We should mention that the incorporation of the electron-hole excitations in the band structure calculations is a nontrivial task and requires an effective two-body approach. It is beyond our capacity now.
7.1.3. Magneto-Optical Spectra
After consideration of the band structure and optical properties, we turn to the magneto-optical spectra. In the polar geometry, where the -axis is chosen to be perpendicular to the solid surface and parallel to the magnetization direction, the expression for the Kerr angle can be obtained easily for small angles and is given by [46] with , the Kerr rotation and the so-called Kerr ellipticity. () is the optical conductivity tensor, which is related to the dielectric tensor through
In Figure 66 we show the experimental [390] and MO Kerr spectra of TmS, as well as the spectra calculated with LSDA, LSDA+, and the electrons in the core. This picture clearly demonstrates that the better description is unambiguously given by the LSDA+ approach. The most prominent discrepancy in the LSDA spectra is the extra peaks between 0 and 2 eV caused by interband transitions involving the hybridized states, which in the LSDA approach exhibit a maximum resonance near . In the LSDA+ approach, the occupied state energies are shifted downward due to the on-site Coulomb interaction . As a result, the transitions involving the occupied states do not take place at small photon energies, and the erroneous peak structures around 0 to 2 eV disappear from the Kerr spectra. The calculations in which the electrons are treated as quasi-core are able to reproduce structure similar to the LSDA+ calculations, but in the wrong positions. Besides, due to the lack of corresponding interband transitions, the off-diagonal part of the optical conductivity is nearly zero, so that a very small Kerr rotation is obtained.
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(c)
Off-diagonal optical conductivity of TmS shows very large values at low energies with a marked extremum in near 0.5 eV and it is almost constant in the 2 to 4 eV energy interval (Figure 66). As a result the shape of the Kerr ellipticity and Kerr rotation spectra in this compound are completely determined by a shape of the function in the (22).
The situation is clearly seen in Figure 67 where we show the theoretically calculated Kerr rotation and ellipticity of TmS using the LSDA+ approximation and the frequency dependence of real and imaginary parts of the function multiplied by a constant to normalize the spectra. Obviously the shape of the Kerr spectra in TmS results mostly from the resonance structure of the function . Actually the first-principles band structure calculations [384] confirm the idea already drawn by Feil and Haas in [391] on the basis of model calculations that the sharp Kerr effect in some magnetic metallic rare-earth compounds including TmS and TmSe is not due to the electronic interband transitions, but rather to the influence of a plasma resonance.
7.2. TmTe
Figure 68 shows the energy band structure and total density of states of TmTe calculated in LSDA and LSDA+ approximations. Although TmTe is known as a magnetic semiconductor, LSDA calculations gave a metallic solution. The LSDA+ calculations predict a correct ground state of TmTe, namely, a magnetic semiconductor with direct energy gap of 0.86 eV at the Γ symmetry point and an indirect gap of 0.58 eV between the top of Tm valence band at the Γ point and the bottom of Tm conduction band at the X symmetry point. Theory produces a somewhat larger energy gap in comparison with the optical measurements of 0.35 eV [365]. Thirteen completely occupied Tm energy bands located between 0.0 and −2.2 eV are hybridized with Te states. The empty 14th energy level is situated around ~5.8 eV above the Fermi level hybridized with Tm states (Figure 68). In other words theory predicts the Tm atom in TmTe to be in divalent state.
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The most striking evidence for the absence of any mixed-valence state in TmTe comes from photoemission measurements. It was shown in [365] that the amount of detectable in UPS measurements depends strongly on the surface condition and that the ratio of increases after cleavage as a function of time from a value ≤6%. Also, the absorption spectrum of vacuum-cleaved TmTe, as derived from the reflectance, shows clear evidence for transitions from in the energy region 0 to 7 eV, but no conclusive indication of transitions from in the energy region 7 to 14 eV [365].
A recent more precise photoemission study of TmTe [373] gives the mean valence value equal to 2.15+ and 2.35+ from study the total yield and off-resonance photoemission spectra, respectively, although the mean valence of the same sample obtained from the result of magnetic susceptibility measurement is 2.017+. The valency of the Tm ion in TmTe from lattice constant considerations was found to be 2.0+ [364]. Thus, it would seem that the trivalent component observed in photoemission measurements mainly comes from the surface. Besides, the valence structure of such samples strongly depends on the stoichiometry. Figure 69 shows TmTe UPS spectrum [373] in comparison with the occupied part of the partial LSDA+ DOS calculated with a multiplet structure of final state taken into account in the same way as for TmS. The multiplet structure consisting of six terms (, , , , , , and ) was taken from [346]. We conclude that the structures between 0.0 and −8 eV binding energy is associated with the final-state multiplet structure. The structures with higher binding energies should be assigned to the final-state multiplet structure of the ions mainly coming from the surface. To check this the energy band structure and DOS of TmTe was calculated using a starting configuration with zero occupation of the 14th and 13th levels ( configuration) and with taking into account a multiplet structure of the final state [384]. As can be seen from Figure 69 the final-state multiplet structure corresponds to structures seen in the −4 to −16 eV energy interval. Hence, the contribution to the peaks at around −5.5 and −7.5 eV binding energy in UPS measurements comes from both the and ions. Besides, there are also contributions to the main feature of the UPS spectrum at 0 to −3 eV binding energies coming from the partly filled 13th level of the ions.
The pressure effects on transport properties of TmTe were investigated by Matsumura et al. [392]. It was found that, at room temperature, the resistivity of TmTe showed an exponential decrease up to 2 GPa, indicating a linear closing of the energy gap (with meV/GPa), followed by an almost pressure-independent metallic regime. In order to investigate the influence of pressure on the electronic structure of TmTe, the self-consistent energy band structure calculations for several reduced lattice constants were performed. It was found a gradual decrease of the energy gap and closing of the indirect gap at Å in a good agreement with experiment. The semiconductor-metal phase transition for pure TmTe takes place at around ~2.5 GPa [392]. The compositionally induced semiconductor—metal transition in the system takes place for with the lattice constant equal to ~6.02 Å [5] (see what follows).
There is no experimental measurements of the MO spectra for TmTe. The measurements have been performed only for the system [46]. The theoretical analysis of the MO spectra of will be considered below.
7.3. TmSe
The simplest argument that TmS is trivalent, TmSe intermediate valent, and TmTe divalent under normal conditions comes from comparing the lattice constants of rare-earth sulfides, selenides, and tellurides as done by Bucher et al. [364]. The lanthanide contraction is the cause for the general trend in the curves, and the standard divalent Sm, Eu, and Yb ions with their larger ionic radius are the obvious deviations. TmTe lies on the divalent curve, TmS on the trivalent one, and TmSe is intermediate, and by linear interpolation between a hypothetical divalent and trivalent TmSe one obtains a valence of . Further evidence that TmSe is intermediate-valence comes from X-ray and ultraviolet photoemission spectroscopy measurements [346, 373]. The photoemission study of TmSe [373] gives the mean valence value equal to 2.79 and 2.68 from study of the total yield spectra and off-resonance photoemission, respectively, although the mean valence of the same sample obtained from magnetic susceptibility measurement is 2.53. It should be mentioned that the total yield spectra reflect more bulk information than photoemission spectra and the values obtained from transport properties or magnetic susceptibility are mostly bulk and not surface sensitive [373].
The ground state of an intermediate valence compound is a quantum mechanical mixture of both the and the configuration on each rare-earth ion. Such compounds need theoretical consideration beyond the mean field one-particle LSDA+ approximation due to possible configuration interaction between different valence states. Although such interaction should be less in Tm compounds in comparison, for example, with mixed-valent Ce compounds due to contraction of the wave function, it can lead to a spontaneous interconfiguration fluctuations (ICFs), introduced first by Hirst [393]. As briefly discussed by Varma [3], at , fluctuations could be either static or dynamic. In the static case the system is spatially “inhomogeneous” in the sense that at inequivalent sites different valence states are present. Examples among the rare-earth compounds are or [346]. Such static charge “fluctuations” have been known for a long time in the -series; , magnetite, being a typical example (see [10] and references therein). In the dynamic case the system shows fast local fluctuations which give an intrinsic width to the levels. At any given site charge fluctuations between the two configurations occur on a time scale , the so-called inconfiguration fluctuation time. The system on time average is “homogeneous,” that is, all sites are equivalent. TmSe is known to be a homogeneous mixed-valence compound [346]. Experiments such as lattice constant and isomer shift measurements which probe the sample on a time scale much longer than will see only one intermediate configuration, but experiments such as XPS or UPS measurements which take place in a time much shorter than (up to 106-107 times shorter [370]) will see the instantaneous picture of a mixture of the ions in the two valence states.
7.3.1. Band Structure
The LSDA+ energy bands and total density of states of TmSe for eV are shown in Figure 70 both for the ferromagnetic and antiferromagnetic ordering for the ions. The electronic structure of TmSe for the ions is very similar to the TmS one with twelve bands fully occupied and hybridized with chalcogenide states. The 14th hole level is completely unoccupied and well above the Fermi level. A hole 13th level is partly occupied and pinned at the Fermi level. The occupation number of the 13th level is equal to 0.27 (valence 2.73+) in good agreement with estimations from the lattice constants (2.75+) as done by Bucher et al. [364] and from UPS measurements (2.79+ and 2.68+ from total yield and photoemission spectra, resp.) [373].
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Figure 71 shows the expanded view of the total DOS of TmSe and TmS both in the ferromagnetic (FM) and antiferromagnetic (AFM) states [384]. An important feature of the FM electronic structure is a high DOS at the Fermi energy in both TmS and TmSe. A large DOS at signals an instability with respect to metamagnetic phase transitions. Indeed, total energy calculations show that the ground state for TmSe as well as for TmS is an antiferromagnetic ordering in agreement with experiment [366, 377]. Through the FM-AFM phase transition a pseudogap at the Fermi level is opened in both TmS and TmSe (Figure 71). The opening of such a pseudo gap may explain the increase of the electrical resistivity below Néel temperature [377, 379, 380], as well as an enormous negative magnetoresistivity associated with the metamagnetic transition to the high-field aligned state and decrease of the Hall coefficient in an external magnetic field [381].
The pinning of a partly occupied 13th level is different in TmS and TmSe. In contrast to TmS, the Fermi level crosses the 13th hole level in the vicinity of its DOS maximum in TmSe, both in the FM and the AFM states. The maximum DOS of the 13th hole level is situated above the Fermi level, as close as 4 meV (~45 K) in the AFM ground state of TmSe. The energy position of the 13th level is in a good agreement with low-temperature far infrared optical measurements by Marabelli and Wachter [394]. According to their measurements the first interband transition appears at about 3 meV. It should be mentioned here that when we speak about partial occupation of the 13th hole level in TmS we mean that such an occupation is due to the hybridization effect between and energy states. The peak position of the 13th hole level DOS in TmS is relatively far away from the Fermi level. A different situation occurs in TmSe where the Fermi level crosses the shoulder of the 13th hole level DOS (see Figure 71); hence, the 13th level is really pinned at the Fermi level. It is a typical situation for mixed-valent crystals.
The Tm monoehalcogenides offer the unique opportunity to follow the evolution of intermediate valence as a function of composition. The driving force is the change of lattice constant upon exchanging the anion. In order to separate the influence of the lattice constant from the influence of the ionic potential of the chalcogenide component on the electronic structure of TmX (X = S and Se), we present in Figure 71 also the DOS of TmSe evaluated with the lattice constant of TmS [384]. The partial occupation of the 13th hole level in this case is similar to the situation for TmS, although the energy positions of the maxima is not the same as in actual TmS. The mean valency of TmSe with the lattice constant of TmS is equal to 2.90+, very close to valency in actual TmS (2.88+). It can be considered as qualitative theoretical support of the conclusion derived in [383] that the application of pressure enhances the state relative to state in the TmSe.
In Figure 72 the partial DOS of the occupied part of the TmSe band structure is compared with XPS measurements [346] for two single crystals with different lattice constants. An off-stoichiometric violet TmSe single crystal, with lattice constant Å, contains almost entirely ions [346]. The theory calculations using a starting configuration with zero occupation of 14th and 13th levels ( configuration) well describe this experimental XPS spectrum.
The XPS spectrum of TmSe with Å has a sizable divalent signal between 0 and −3 eV binding energy. The middle panel of Figure 72 shows the theoretically calculated DOS of the Se taking into account the multiplet structure of the final state. The bottom panel shows the experimental XPS spectrum for Å, in comparison with the sum of and DOSs in the proportion of fifty-fifty. These results suggest that the valency of the sample with Å, is close to 2.5 as comes from the analysis of the DOSs. Of course it is difficult to make quantitative conclusions about the possible Tm configuration in TmSe from comparison of theoretically calculated DOS with XPS or UPS spectra. From such a comparison we can only derive an energy position of final-state multiplet structures from and ions. The XPS and UPS spectra are strongly affected by the transition matrix elements which have been omitted in the consideration for simplicity. Besides, the relative intensities of and ion final-state multiplet structures depend on the excitation photon energy. This was shown in [373] where the intensity ratio between the trivalent and divalent components in Tm monochalcogenides changes significantly depending on resonance or off-resonance conditions. Finally, UPS and XPS spectroscopies are strongly surface-sensitive methods. The escape depth of a photoelectron with kinetic energy of a kilovolt is about 15 Å. For the softer radiation typical for the UPS measurements (≤100 eV) the escape depth is only about 4 Å [4]; hence, only the surface layers are probed. A recent advance in our understanding of mixed-valent photoemission comes from the recognition that surface spectra can be markedly different from that of the bulk. In particular the valence at the surface can be very different [4].
In the optical reflectivity measurements the depth of penetration is given by the inverse absorption coefficient and typically amounts from 102 to 103 Å. This means that the optical measurements are not so surface sensitive.
7.3.2. Optical Spectra
Figure 73 shows the calculated diagonal part of the optical conductivity and the optical reflectivity of TmSe treating the states as (1) fully localized ( in core), (2) itinerant (LSDA), and (3) partly localized (LSDA+) in comparison with experimental data [389]. The calculations treating electrons as core electrons place the zero crossing energy of at higher energies in comparison with the LSDA+ calculations and as a result give a wrong energy position for the plasma resonance which determines a deep minimum in the optical reflectivity (Figure 73). Due to the wrong position of energy bands in the LSDA calculations, this approximation is not able to produce the correct optical reflectivity in the infrared spectral region. Figure 73 clearly demonstrates that the better description of the optical reflectivity spectrum is given by the LSDA+ approach. The interband transitions play an essential role in the fast decrease of the optical reflectivity in 0 to 0.5 eV energy interval.
7.3.3. Magneto-Optical Spectra
In Figure 74 we show the experimental [263] and MO Kerr spectra of TmSe, as well as the spectra calculated with LSDA and LSDA+. The better description is unambiguously given by the LSDA+ approach. The most prominent discrepancy in the LSDA Kerr spectra is the extra peak at 0.5 eV which is caused by extra structure present in the dielectric tensor. Responsible are interband transitions involving the hybridized states, which in the LSDA approach exhibit a maximum resonance near . In the LSDA+ approach, the occupied state energies are shifted downward due to the on-site Coulomb interaction . As a result, the transitions involving the occupied states do not take place at small photon energies, and the erroneous peak structure around 0.5 eV disappears from Kerr spectra.
Some experimental results [5, 394–396] indicate that TmSe could be a narrow-gap semiconductor below the Neel temperature. Evidence for a hybridization gap comes from the activated behavior of the electrical resistivity [4] and from a large negative value of the Hall coefficient at 3.5 K [4], suggesting fewer than 1018 carriers per . Another evidence that stoichiometric TmSe might be a narrow-gap semiconductor comes from point contact measurements [395]. The dynamic resistance / which for intermediate-valence materials is proportional to has a peak at in the AFM state. Such a peak disappears in an external magnetic field above 10 kOe where TmSe exhibits a ferromagnetic order. A maximum in corresponds to a minimum in —a gap or at least a pseudogap. The estimations from the activation energy in electrical resistivity measurements and from point-contact spectra show a possible gap of about 1 to 2 meV [5].
On the other hand, some experiments indicate that there may not be a gap but rather a pseudogap, and the hybridization does not occur over whole Brillouin zone. The electrical resistivity is raised only about one order of magnitude through the FM → AFM phase transition [5]. Direct optical measurements by Battlog et al. [397] show a metallic reflectivity in Se with a reflectivity edge which shifts about 0.5 eV as varies from thulium deficiency to excess. Such studies as a function of stoichiometry give convincing evidence that the intrinsic TmSe behavior is metallic. More recent optical measurements by Marabelli and Wachter [394] show that during the measurements they always found a free carrier behavior for the lowest energies, then a gap or a pseudogap followed by a first interband transition at about 3 meV.
In our LSDA+ band structure calculations of TmSe we used as a starting configuration with zero occupation of 14th and 13th levels. In the process of self-consistent relaxation, the 14th hole level is situated well above the Fermi level, but the initially empty hole 13th level becomes partly occupied due to pinning at the Fermi level with occupation number equal to 0.27 (valence 2.73+) producing a metallic AFM-ordered ground state with a pseudo gap at the Fermi level. Such an energy band structure well describes the energy distribution curve of the UPS spectrum, as well as the optical and MO spectra of TmSe (see Figures 72, 73, and 74, resp.). We should mention that the more sophisticated LDA++ method [398] which takes into account the energy dependence of the electron self-energy also failed to obtain an insulating AFM ground state in TmSe. The possible appearance of such an energy gap in TmSe might be caused by both hybridization and exciton effects due to the Coulomb attraction of the conduction electron and hole [398]. This effect is not described in the LDSD+ and LDA++ methods. This mechanism requires further theoretical investigations. Additional experimental low-temperature optical ir measurements on good quality single crystals of TmSe are highly desired.
7.3.4. Summary
In contrast to LSDA, where the stable solution for TmTe is a metal, the LSDA+ method gave an insulator with an indirect energy gap of 0.58 eV. LSDA+ theory predicts that the thulium ion in TmTe is in an integer divalent state. It also shows a gradual decrease of the energy gap with reduction of the lattice constant. The gap is closed at Å in a good agreement with experimental measurements of TmTe transport properties under pressure and the compositionally induced semiconductor-metal transition in the system.
For the ions of TmS and TmSe twelve bands are fully occupied and hybridize with chalcogenide states. The 14th hole level is completely unoccupied and well above the Fermi level. The initially empty hole 13th level in the process of self-consistent relaxation becomes partly occupied with DOS maximum situated in close vicinity of the Fermi level in TmS and TmSe. A fundamental aspect of this observation is the partial occupation of the 13th state to be a robust property of TmS and TmSe compounds: it happens irrespective of the precise value of . The positions of the 13th and 14th hole levels in TmS and TmSe are in good agreement with BIS and optical measurements. The degree of occupation and position of the partly occupied 13th level with respect to the Fermi level is different in TmS and TmSe. In TmS the hole level is almost empty and situated significantly far from the Fermi level. Such a situation is appropriate for achieving the Kondo lattice scenario. In TmSe the upper hole 13th level is pinned at the Fermi level; therefore, TmSe is expected to be an intermediate-valent compound in agreement with experimental data. The occupation number of the 13th hole level is equal to 0.12 and 0.27 (valency 2.88+ and 2.73+) in TmS and TmSe, respectively, in a good agreement with the experimental estimates from lattice constant and XPS and UPS measurements.
The LSDA+ theoretical calculations describe well the measured XPS and UPS Tm monochalcogenides spectra only after taking into account the multiplet structure of final and states for and ions, respectively. It was shown that the structures in the XPS and UPS spectra of TmS and TmSe between −4.5 and −16 eV binding energy should be assigned to the final-state multiplet structure derived from twelve fully occupied bands (), and the structures between 0.0 and −4.5 eV are associated with the final-state multiplet structure of the partly occupied 13th state.
The MO spectra of TmX (X = S, Se, Te) are very sensitive tools for drawing conclusions about the appropriate model description. On account of the calculated MO spectra, we conclude that TmS and TmSe MO spectra are best described using the LSDA+ approach. The shape of the Kerr spectra in TmS and TmSe is mostly due to a resonance structure of the function due to a steep plasma edge. The analysis indicates that the available experimental Kerr spectra for is a complex mixture of the divalent and trivalent Tm ion spectra.
8. and Related Compounds
The rare-earth pnictides (X = P, As, Sb, Bi) exhibit unusual physical properties [399–406]. The high-temperature phases of these compounds have the cubic anti- structure with space group . The Yb ions occupy the P sites with Wyckoff positions , and the X ions occupy the Th sites with special Wyckoff positions , fixed by symmetry ([407], see Figure 75(a)). All Yb-atoms are aligned on four families of chains oriented along the four diagonals of the cubic unit cell ([408], Figure 75(b)). All four ytterbium pnictides have anomalously large lattice constants (, 8.788, 9.322, and 9.573 Å for X = P, As, Sb, and Bi, resp.) [399, 400]. Because the pnictide ion is trivalent, three of the four Yb ions have a filled shell (valency 2+), while one ion is in a 4 (valency 3+) configuration. When all Yb sites are equivalent, the hole in the shell is moving between different Yb ions and the system is a mixed-valent metal. Its average Yb-valence is rather close to the observed one (), obtained from the Mössbauer experiments [401].
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The most interesting material is . At about K it undergoes a weak first-order phase transition with a trigonal distortion. This transformation was clearly established by susceptibility measurements [399], the Mössbauer spectra [401], polarised neutron diffraction [409], and elastic constant measurements [410]. At the structural transformation, the crystal shrinks in a volume-conserving way along one of the four Yb-chain directions (, say). The resulting trigonal unit cell with the trigonal angle has the short chain along its main diagonal. The centered trigonal space group is now R3c with two inequivalent Yb sites at Wyckoff positions , and two further inequivalent Yb sites at Wyckoff positions 6b, 1, as well as two inequivalent As sites at Wyckoff positions 6b, 1. The distortion is accompanied by charge ordering with ions occupying the short chains [406]. So the electronic state of changes from a valence-fluctuating state in the cubic phase to a charge-ordered state in the trigonal phase, although the charge ordering is not complete [401, 409]. The ions have a closed shell with no spin magnetic moment. The ions have the configuration with spin magnetic moment equal to one. Inelastic neutron scattering experiments on revealed the existence of low-energy excitations that are characteristic of a one-dimensional antiferromagnetic coupling at low-temperatures [409].
Below 100 K, exhibits heavy-fermion behavior: the resistivity shows a behavior ascribed to electron-electron interaction involving the heavy quasiparticle band, the Sommerfeld coefficient of the electronic specific heat has a relatively high value of about 200 mJ mol−1 K−2, and the extrapolated magnetic susceptibility at 0 K has a rather large value emu/mol ([399]). The Sommerfeld-Wilson ratio is found to be of the order of unity, indicating Fermi-liquid behavior. Below 2 K and for moderate applied magnetic fields (>2 T), the “high field” magnetic susceptibility of drops considerably as compared to the low field value [411]. There is also a rapid decrease observed in the specific heat at an applied field of about 1 T [402], both observations indicating the destruction of the heavy electron behavior.
The Hall coefficient of , extrapolated to , is equal to (see [399]). It would correspond to a carrier concentration of about 0.001 per formula unit if only one type of carriers was present.
The pressure effects on transport properties of were investigated by Okunuki et al. [412] and by Môri et al. [413]. A clear increase of the carrier concentration is observed with increasing pressure which leads to a rapid decrease of the resistivity . The maximum in the temperature dependence of both and also decreases with pressure. However, the inverse Hall mobility, that is, the resistivity divided by the Hall coefficient, is found to increase with increasing temperature without any anomaly in the low-temperature phase even under high-pressure. This demonstrates that the mobility is not affected by pressure.
Summarizing all the experimental data, we can conclude that there is a strong dependence of the transport properties of on doping, pressure, and sample preparation, but the specific heat and magnetic susceptibility do not change very much. This observation suggests that is not an ordinary heavy-fermion system. The latter are usually interpreted within the context of a Kondo lattice model. The heavy quasiparticle bands are thought to originate from Kondo resonance states at the Fermi level which evolve into coherent band states below a characteristic temperature. However, this mechanism leads to a similar behavior of the specific heat coefficient and the carrier number as functions of doping. As explained above the opposite behavior is observed which is a strong argument against the Kondo scenario in this class of compounds.
The electronic structure of has been investigated experimentally by means of photoemission [414], X-ray bremsstrahlung isochromat spectroscopy [415], optical properties [416–418]. The optical measurements [416, 417] show a strong temperature dependence of the optical reflectivity in the far infrared energy region below 10 meV. The plasma frequency derived from optical measurements [418] is very small. It varies from 0.08 eV for 10 K to 0.14 eV for 70 K indicating again an extremely small carrier number. Photoelectron spectroscopy in the X-ray and ultraviolet ranges (XPS and UPS) provide information on the energy position of and states in charge-ordered . Structures in UPS and XPS spectra with binding energy between 0 and 4 eV were identified [414] to be the spin-orbit doublet of the final states and the structures between 6 and 13 eV to be the multiplet structures of the final states. The low-temperature photoemission also does not show any evidence for Kondo resonance states close to the Fermi level, confirming the exclusion of the Kondo scenario for .
Two approaches have been proposed to explain the properties of . One is based on a one-electron picture and was applied by Ochiai et al. [399] in form of a four-band model and by Kasuya [419] in form of a two-band model. A characteristic feature of this approach is a hole band of As states and a Yb band with a high density of states near the Fermi level. The second approach treats the electrons as being strongly correlated [420–422]. Charge ordering of the ions and the associated structural phase transition are a consequence of reducing the sum of the Coulomb repulsion and exchange to a minimum and are described by a band Jahn-Teller effect of correlated electrons. The observed heavy-fermion behavior is ascribed to spin-like excitations in the chains.
These two approaches have been combined in [423] by studying the electronic structure and the physical properties of in the trigonal low-temperature R3c phase within an ab initio band structure approach which takes strong correlations into account. This was achieved by applying a local spin density approximation to the density-functional theory supplemented by a Hubbard term (LSDA+). The electronic structure of the related compounds (X = P, Sb, Bi, and ) was also considered.
8.1.
The LSDA total DOS of is shown in Figure 76. The occupied part of the valence band can be subdivided into three regions separated by energy gaps. The bands in the lowest region have mostly As character with some amount of Yb character mixed in. The next group of bands is formed by As states with little admixture of Yb and states. The large narrow peak close to the Fermi energy is formed by Yb states. Unoccupied bands of Yb are separated from the states by an energy gap, a characteristic and important feature of the ytterbium pnictides. The position of the LSDA states close to the Fermi energy is, on the other hand, in contradiction to the findings of XPS and UPS experiments [414].
The LSDA+ band structure calculations in [423] were started from the configuration for three ions, where all 14 on-site energies are shifted downwards by , and from the configuration for one ion with 13 on-site energies shifted downwards by and one level shifted upwards by this amount. The energies of occupied and unoccupied bands are separated by approximately .
The LSDA+ energy bands of AF for eV and eV are shown in Figure 77. For three divalent Yb ions the bands are fully occupied and hybridize with As states in the energy range between −0.5 and −2.5 eV. They are split due to spin-orbit coupling by eV. For the trivalent Yb ion, thirteen electron bands per ion are well below the Fermi level and separated from a hole state by the correlation energy . One hole band per ion, doubly degenerate due to AF ordering, appears closely below the top of the As band. Since the As band is separated from the Yb band by an ordinary band gap, the Fermi level must be pinned at the bottom of the hole band. This feature in combination with the small mass of the As electrons close to the top of the band appears to be a clue feature for the physics of the ytterbium pnictides. Due to the very small phase space for hybridization and the very small Yb –As orbital overlap, the DOS peak of the hole band is as narrow as 0.007 eV right above the Fermi level. It is now clear why the usual Kondo lattice scenario is inappropriate for these pnictide compounds. For a Kondo resonance to develop both the occupied and empty -states must be sufficiently far away from the Fermi level. Quite opposite to this situation the (almost) empty level is pinned slightly above the Fermi energy. But due to the very small phase space for hybridization around the Γ point one still has an almost stable moment of the nearly integer occupation of the shell.
Since the binding energy of the ions is larger than 0.5 eV and hence larger than the Yb –As orbital hybridization energy both in experiment and in the calculated band structure, the shell of the ions has been treated as a core shell in the following detailed numerical analysis. It has been checked that this simplification does not affect the issue. Therefore, we are left with a charge balance between Yb states of the ions and pnictide states only. Any charge transfer between these states causes a change in the Hartree potential which is governed by the bare Coulomb integral of the state being as large as 30 eV. Thus, an artificial shift via tuning of the hole level by 3 eV, say (corresponding to a change of itself by 6 eV), will completely be compensated by a charge transfer as small as 0.1 electron charge. For this reason the hole level, to which the Fermi level is pinned, is itself very rigidly pinned close to the top of the pnictide band.
In Figure 78 the band structure in the vicinity of the Fermi level is shown for eV. It corresponds to a ground state with a hole pocket around the Γ point () holding 0.0058 As holes per formula unit. For chosen values , 7.0, 9.6, and 9.8 eV the obtained hole numbers are 0.0717, 0.0225, 0.0058, and 0.0005, respectively. Only for eV the As band would be filled and the Fermi level would lie in a gap between this band and the hole state. This generic feature is obtained independent of whether the filled shell of the ions is treated as core or as valence, whether AF of ferromagnetic order is assumed on the chains or whether spin-orbit coupling is taken into account or not, all the involved energies being small compared to the unscreened . Figure 79 shows the obtained partial DOS close to the Fermi level for a number of cases.
The carrier density in at low temperature is extremely low, for which the following findings give evidence: (1) a large value of the resistivity up to 10 m [399], (2) a very low plasma frequency obtained from optical reflectivity [418], (3) a large value of the Hall coefficient [399] which corresponds to about 0.001 holes per ion, assuming the single carrier model. is a compensated semimetal, so the number of As holes exactly equals the number of excess Yb electrons in the partially filled hole level. However, the mobility of heavy electrons is assumed to be negligible in comparison with the mobility of As electrons [399]. So the transport properties of are mostly determined by the number of As holes. In the analysis of [423], a carrier number of 0.001 per formula unit would result from a value between 9.6 and 9.8 eV which would not be in contradiction with photoemission.
The small mass at the top of the pnictide band results in a very low DOS of 0.015 states per eV, atom, and spin, at the hole level for eV. This means that there are very few band states to broaden the level by hybridization. The width of the hole state equals to about 0.007 eV (80 K) and decreases with increasing . The total DOS at the Fermi level, resulting essentially from the hole states, yields for eV a large band structure contribution to the Sommerfeld constant of mJ mol−1K−2. The calculated is substantial, yet it corresponds only to the experimental value in a sufficiently strong magnetic field which suppresses magnetic moment fluctuations [402]. Since , although a semiconductor, has an even larger value of the Sommerfeld constant than , a large part of must be due to fluctuations of the magnetic moments in charge-ordered chains. Beyond LSDA+, further many-body interactions need to be invoked to account for the full Sommerfeld constant of the specific heat [420, 424].
8.2. (X = P, Sb, and Bi)
Figure 80 shows the energy band structure and total density of states near the Fermi level for , , and calculated in the trigonal R3c AF crystal structure in the LSDA+ approximation with eV. Only , and reveal the charge-ordering cubic-to-trigonal structural transformation. The other two compounds remain in the cubic structure down to lowest temperatures with the ions being randomly distributed among the four chains. Such a valence fluctuating system is presently outside the scope of our investigation.
(a)
(b)
(c)
(d)
The main trend in the electronic structure of the sequence of compounds (X = P, As, Sb, or Bi) results from the characteristic trend in the pnictide wave functions and from the systematic change of the lattice parameters. The counteraction of screening by inner atomic shells and of relativistic effects leads to the characteristic trend in the position of the atomic state and hence of the center of gravity of the pnictide band, first increasing from P to As and then monotonically decreasing to Bi. The bandwidth is monotonically increasing from P to Bi due to the increasing extension of the atomic wave function, although the lattice constant increases too (see Table 10). Therefore, if one moves from to through the series, the unoccupied level moves from below towards the top of the pnictide band and beyond, implying a reduction of metallicity and finally a transition to semiconducting behaviour, which is experimentally found in for [400]. Figure 80 shows the energy band structure of the series, including also, . In this compound, treated as ordered, two AF ordered ions are no longer chemically equivalent and the system becomes ferrimagnetic. This leads to a splitting of the hole bands. These bands are already well above the top of the valence band.
Experimentally, and show the typical valence-fluctuating behaviour [399]. Their energy band structures calculated for hypothetical trigonal R3c symmetry differ significantly from that of . With the increasing pnictide band widths, already in the indirect gap between the top of the Sb valence band and the bottom of the Yb conduction band is closed (Figure 80). In the direct gap has also disappeared due to further broadening of the Bi 6 conduction band. However, there is still no overlap between the partly filled narrow Yb band and the Yb conduction band in both compounds.
8.2.1. Summary
Using the LSDA+ approach to band structure calculations with a value adjusted to experiment but close to theoretical estimates, it was found a band gap between the As band and the Yb band in . As a consequence, a very narrow marginally occupied hole band is pinned close to the top of the As valence band via the charge balance between Yb and As which is governed by the large (~30 eV) bare Coulomb integral of the Yb state. The same charge balance pins the Fermi level close to the bottom of this hole band which has a width of 0.007 eV (80 K). It lead to an extremely low carrier density in . The Fermi surface of consists of two almost spherical sheets: a hole pocket of As states with a relatively small effective mass, centered at the Γ point of the BZ, and an electron ellipsoid of Yb states with a relatively heavy mass, centered on the symmetry line Γ-P.
The systematic trends in the position and width of the pnictide band when going through the pnictogen group of the Periodic Table leads to a transition to semiconducting behavior towards the light pnictogen end with a charge transfer gap between the pnictide band and the Yb state, and to an increasing carrier number and hence increasing metallicity with valence-fluctuating Yb ions towards the heavy pnictogen end. Already in semiconducting behavior is found. In and in the band gap between the pnictide valence band and the Yb conduction band is closed.
For , the LSDA+ band structure calculations provide a two-band model of the electronic structure: (1) a wide, nearly fully occupied As valence band and (2) a very narrow, marginally occupied Yb band, very weakly hybridized with the As band in a small space region near the Γ point of the BZ. Pressure, doping and so forth. may slightly change the relative position of these two bands and hence strongly affect the low carrier density and the transport properties. But the shell of the ions is little influenced as long as the charge order is maintained.
In the LSDA+ band structure calculations the compounds have been treated as ideal systems with perfect charge and AF-order. The real situation is much more complicated. shows no magnetic ordering down to a very low temperature of 0.2 K. However, experimental evidence for existence of short-range AF correlations was found. An external magnetic field strongly affects the magnetic excitations suppressing the heavy-fermion properties of . Going from to , the number of ions increases, the degree of charge and AF ordering also increases, and despite of the decrease of the number of free carriers ( is a semiconductor) the heavy-fermion properties are more pronounced which is reflected in the increasing value of the Sommerfeld constant from about 200 mJ mol−1 K−2 in to 250 mJ mol−1 K−2 in . Going to heavier pnictogen ions, metallicity increases and the tendency to moment and charge order is lost, and a typical mixed-valence behavior is found instead.
The large value of the semimetal cannot be incorporated into Landau’s Fermi-liquid theory for the following reason. In Landau’s theory it is essential that the linear specific heat coefficient is related to the density of states at the Fermi level which depends on the quasiparticle masses. This relation does not hold here as seen by realizing that a large value is found even in the absence of any Fermi surface like in for . This is not surprising as the huge value can be assigned to spin excitations in the Heisenberg chains and can therefore be unrelated to the quasiparticle excitations near the Fermi surface. It depends on the characteristic energy for the fluctuations of magnetic moments in the charge-ordered chains which is given by the superexchange of moments along chains via pnictide orbitals. Note that only the effective moments of the lowest crystal-field doublets are relevant here. We speculate that, if the complete Fermi surface and the effective masses of could be measured, one would find that they do not explain the specific heat in contradiction with Landau’s Fermi-liquid theory. Therefore, this concept requires a generalization. One of the strong points of Landau’s theory is that it is a phenomenological approach, which does not require a microscopic model for a given material. It is within that spirit that a generalization is suggested by postulating in addition to the charged fermions (electrons or holes) a liquid of neutral fermions with a density of states N*(0). This density of states is fitted to the value of the specific heat. The underlying physical picture is, of course, that the magnon-like spin excitations in the chains, although of bosonic character, can be transformed into charge neutral fermionic excitations giving rise to the large value. But, as pointed out above, we are dealing with a phenomenological theory, and therefore no microscopic justification of the postulate is required. A liquid of neutral fermions for the description of a metallic system was suggested before by Kagan et al. [425] in connection with Kondo lattices. In the present case, the neutral fermions do not contribute to electric transport, but, for example, to the thermal conductivity. They contribute also to the compressibility and to the spin succeptibility. The observed behavior at low temperature [399] with cm/K2 has to be interpreted as resulting from the scattering of the charged quasiparticles off the neutral fermions. A more detailed analysis of these features is left to a future investigation.
9. Sm and Eu Pnictides and Chalcogenides
Cubic with the anti- structure undergoes a first-order transition into a trigonal phase at about 260 K. This change has been ascribed to a charge-ordering transition from the thermal valence-fluctuating state into a static mixture of di- and trivalent sites as one of the diagonals of the cube shrinks by approximately 1.4% [405, 426–428]. In charge-ordered , smaller ions occupy the short chains [428]. Similar to , each magnetic chain is isolated from other chains by ions for which the total angular momentum (J) equals zero. However, shows a three-dimensional antiferromagnetic order at 2.7 K [429] as opposed to , where a one-dimensional antiferromagnetic coupling at low temperatures has been predicted [420] and later discovered [409]. At this point, it is of great interest to characterize the nature of the phase transition occurring in , because the physical properties of its distorted phase have been found to differ from those of . In particular, no maximum occurs in the temperature dependence of the electrical resistivity, nor is there any appreciable linear term in its electronic specific heat.
Contrary to , two other samarium pnictides and show no evidence of charge-ordering in a wide temperature range [427]. The change of the character of charge ordering in due to pressure has been studied in [427, 430]. With increasing pressure the resistivity anomaly at the charge ordering transition moves to lower temperatures, becomes weaker, and completely disappears at 2.8 GPa. Above that pressure the crystal undergoes a first-order, isostructural phase transition characterized by an abrupt decrease of the resistance by a factor of three and a volume by about 10%. The behavior of the electrical resistivity in the high-pressure phase (at 3 GPa) of is similar to that of and [427]. The effect of high pressure can be reproduced by substitution of Bi atoms by smaller Sb atoms. Such an investigation has been reported in [431]. It was found that, with increasing Sb content in the system, the carrier concentration decreases and the charge-ordering temperature slightly increases, while by applying pressure the ordering temperature decreases. This relationship between the substitution and pressure effect in is very similar to that in . So, it was suggested that is a semimetal in the same way as . Although the substitution effect may be different from the pressure effect, both effects finally lead to enhancement of the state relative to state. The electronic states of and were studied with photoemission spectroscopy in [432, 433].
Recently experimental evidence for charge ordering in has been reported. A first following from this result is the observation of trigonal distortion with Å, , which would indicate a periodic arrangement of the and ions [434]. Important information concerning the charge ordering of was given by the Mössbauer spectroscopy measurements done by Wortmann et al. [435]. They found two absorption peaks separated clearly below K corresponding to the di- and trivalent Eu ions. Above 340 K, these two peaks suddenly unite and the line width narrows with increasing temperature. Therefore, they concluded that is a thermal valence-fluctuating compound which goes into a charge-ordered state below 340 K. Discontinuous changes corresponding to the structural transition are observed in the magnetic susceptibility, too [429]. However, the change of the magnetic susceptibility of at the structural transition temperature is opposite to that of that is, the magnetic susceptibility of is larger in the low-temperature phase while that of is smaller. The temperature dependence of the specific heat of shows that, at the structural transition temperature, a sharp -like peak is observed [429]. This indicates that the structural transition is of first order. orders ferromagnetically at K in contrast to and which possess antiferromagnetic order at low temperatures. Anomalies in the structural, transport, and thermal properties in associated with this transition are similar to those found in and .
The samarium chalcogenides (X = S, Se or Te) with the cubic structure are well known as typical examples of valence-fluctuation compounds, where two different valence ions, and , coexist [436]. Such a possibility was mentioned already in the early work of Picon et al. [437]. They noted that the lattice constants of and are too large in comparison with those of the trivalent compounds, indicating that cations with two different valence states 2+ and 3+ coexist in a ratio of 1 : 2.
Unlike most other -type rare-earth chalcogenides, which are trivalent and metallic [364], the compounds behave as semiconductors, with a room-temperature electrical resistivity already of the order of 1 Ωcm. The activation-type temperature dependence of the dc resistivity has a unique value of the activation energy eV for (X = S, Se, or Te) [315, 438]. The optical measurements reveal a direct energy gap in and equal to 0.2 eV and 1.7 eV, respectively [439, 440]. The analysis for the dielectric response confirmed that is an insulator, that is, without free carriers at low-temperature [441]. But the gap is so small that it is easily smeared by imperfections like in La-doped SmB6 [427]. From X-ray diffraction experiments [436], both types of Sm ion were found to occupy the same crystallographic site. The magnetic susceptibility of is explained by a sum of the susceptibility of the Van Vleck term for with (0 K) and (400 K) and of the Curie term for with in the coexistence ratio 1 : 2 [442]. Assuming ideal stoichiometry, simple charge balance for the nominal formula implies that no free carriers are available to populate the conduction band, which explains the lack of metallic conduction observed experimentally. Thermally activated electrical transport takes place, however, through the hopping of electrons among the rare-earth sites [443]. Thus, near room temperature, the Sm ions fluctuate rapidly between two configurations and , giving rise to the so-called “thermal valence fluctuations.” This mechanism differs markedly from the “quantum valence fluctuations” occurring in homogeneously mixed-valence compounds [3–5, 7]. Here, the fluctuations slow down drastically as decreases, as evidenced by the upswing in the transverse nuclear relaxation rate on cooling below 160 K [444] or the frequency-dependent stiffening of the elastic constants, [445] and an activation-type temperature dependence of the relaxation time, . The relaxation time corresponding to the hopping rate in the thermal motion of the electron from to neighboring ions in becomes longer and longer on lowering the temperature; however, no sign of a phase transition to a charge-ordered state has been found. On lowering the temperature, the fluctuation of the electrons freezes gradually into a charge glass state, which is characterized by the random distribution of and ions in space. In fact, it has been reported that the broad peaks of the magnetic susceptibility and specific heat around K in occur at the transition into the spin-glass state because of the random ordering of the magnetic moments of and ions [446].
This result is in contrast with the low-temperature properties of the isomorphic compound. This compound possesses a first-order phase transition near K [447]. The transition exhibits the configurational entropy of an order-disorder transition. The structural changes at the phase transition of were found to be very small compared, for example, to these of the second-order structural phase transition in [447]. The carrier concentration drops by roughly 3 orders of magnitude in upon cooling below [448]. has also a phase transition to a ferromagnetic state below K [449]. A recent synchrotron X-ray diffraction study for single crystals of has revealed that a -type structure transforms to a charge-ordered one at K [450]. In the crystal structure, all ions mix with half the in the 8 sites, and the remaining ions occupy the 4 sites.
No such effect has been observed in the Sm chalcogenides down to temperatures of less than 1 K. This intriguing result has raised interesting speculations as to the nature of the low-temperature state in the compounds [403]. From the AC conductivity, it has been suggested that, as thermal fluctuations die out at low temperatures, tunneling of electrons between neighboring sites may become the dominant transport mechanism. It is known that the tunnel motion of the electrons is relevant when the initial and final states possess nearly equal energies [7]. Various spectroscopic probes (Mössbauer effect [451], NMR [444], SR [452]) have been used to determine the charge and magnetic response of these compounds with different characteristic time scales. It now seems most likely that, in , the moments freeze at low temperature into a spin-glass state [444, 446], possibly associated with a static, or quasistatic, spatial disorder of the two configurations. According to this interpretation, the huge linear term, J K−2/mol and J K−2/mol, observed in the low-temperature specific heat in and , respectively [453], can be ascribed to magnetic disorder rather than to heavy-fermion phenomena as proposed initially.
Why does favor the charge glass state and does not exhibit charge ordering with the usual first-order transition with symmetry-breaking character like or ? To answer this question, the microscopic details about the electron states and their degree of hybridization with conduction states are highly relevant.
Crystal Structure
The high-temperature phases of (R = Sm, Eu; X = As Sb, Bi) compounds have the cubic structure with space group (no. 220). The R ions occupy the P sites with Wyckoff positions , (), and the X ions occupy the Th sites with special Wyckoff positions (, , ) [454]. All R-atoms are aligned on four families of chains oriented along the four diagonals of the cubic unit cell [408].
The high-temperature phases of and (X = S, Se, or Te) compounds have the bcc structure with space group (no. 220). Conventional unit cell of includes four formula units. Both ions and in occupy crystallographically equivalent 12 sites (/8, , ) with symmetry. S occupies the sites (). Only the -coordinate of sulfur ( parameter) is a variable among positional parameters. We used the experimentally determined values of , 0.0722, 0.0724, and 0.0724 for , , , and , respectively [454]. It gives a slight deviation from an ideal structure (). An Eu ion is coordinated by eight sulfur ions in a distorted cube while a sulfur ion is coordinated by six Eu ions.
A recent synchrotron X-ray diffraction study for single crystals of has revealed a low-temperature charge-ordered structure with tetrahedral symmetry and a space group of (no. 122). The cell dimensions are Å and Å [450]. Eu ions occupy crystallographically two nonequivalent positions, namely, () and () sites. S ions occupy the sites () [450]. Both Eu sites are coordinated by eight sulfur ions. The sites are distributed as in the diamond structure. The mean Eu–S distance for the sites is about 0.3% larger than for the sites.
9.1.
The LSDA+ partial DOSs of antiferromagnetic (AF) are shown in Figure 81 [455]. In order to imitate the nonmagnetic () ground state of ion the exchange-correlation potential is taken to be the same for both spin states within the corresponding atomic spheres. For three divalent nonmagnetic Sm ions, six energy bands per ion are fully occupied and hybridize with Bi states at around −2.0 eV below Fermi energy. The other eight divalent Sm energy bands are situated far above the Fermi level at 6.5 eV and hybridize with Sm states. Both the occupied and empty states are very narrow which indicates that their hybridization with Bi and Sm states is rather weak. For the trivalent Sm ion seven spin-down electron bands per ion are well above the Fermi level and hybridize with Sm states. Five spin-up states are below the Fermi level situated right in the energy gap between Bi and states (not shown). The other two spin-up energy bands for the trivalent Sm ion, doubly degenerate due to AF ordering, appear just below the top of the Bi band. One of them is completely empty and above the Fermi energy at around 0.15 eV, but the other one is pinned to the Fermi level. The 6th and 7th spin-up energy bands have different orbital characters, and , respectively, and their splitting is mainly caused by the nonspherical part of the Coulomb interaction.
The pinning of the 6th spin-up state to the Fermi level is a robust feature of the electronic structure of the compound. As an example, we present in Figure 82 the energy bands of for different values of Coulomb parameter . The 6th spin-up state just slices near the top of the Bi band when is varied from 3 to 10 eV. Only for eV does the Sm band become empty. Such pinning of the state to the Fermi level may be explained by the charge balance between Sm states of the ions and pnictide states. This feature in combination with the small mass of the Bi electrons close to the top of the band appears to be a key point for the physics of the Sm pnictides.
(a)
(b)
(c)
In Figure 82 for drawing of the bands we used the so-called fat-bands representation. The size of the circles indicates the degree of the orbital character in a band. Such a representation can help to visualize also the hybridization between Sm and Bi states. The largest Sm -Bi hybridization was found to be near the Γ symmetry point in the Γ-P direction. Due to the very small phase space for hybridization and the very small Sm -Bi orbital overlap, the DOS peak of the 6th hole spin-up band pinned at the Fermi level is as narrow as 0.01 eV.
This situation is similar to that found in the charge ordering of [423], where a very narrow marginally occupied Yb hole band is also pinned close to the very top of the As valence band via the charge balance between Yb and As. One should mention, however, that there are also some important differences. There are two energy bands crossing the top of the Bi band in but only a single one in the compound. The latter case corresponds to a ground state with a hole pocket around the Γ-point () holding 0.0058 As holes per formula unit. In the case of a hole pocket around the Γ-point contains 0.25 Bi holes per formula unit. As a consequence the carrier concentration is relatively large in . However, the most prominent difference in the electronic structure of the in comparison with the compound is the value of the spin moment of the corresponding magnetic ions. The ions occupying short chains in have the configuration with an effective spin of . This leads to appearance of one-dimensional spin chains with antiferromagnetic coupling at low temperatures [409]. The trivalent ions with the configuration have a spin moment , and possesses a three-dimensional antiferromagnetic order [429]. The Fermi surface of consists of two closed hole pockets of Bi states centered at the Γ point and two electron ellipsoids of Sm states centered at P and A symmetry points. The corresponding Fermi surface of consists of a hole pocket of As states centered at the Γ point and an electron ellipsoid of Yb states centered on the symmetry line Γ-P.
The mobility of heavy holes is assumed to be negligible in comparison with the mobility of pnictide electrons. So the transport properties of are mostly determined by the number of pnictide holes.
9.2. and
The main trend in the electronic structure of the sequence of compounds (X = As, Sb, or Bi) results from the characteristic trend in the pnictide wave functions and from the systematic change of the lattice parameters. The counteraction of screening by inner atomic shells and of relativistic effects leads to the characteristic trend in the position of the atomic state, and hence the center of gravity of the pnictide band decreases from As to Bi. The bandwidth is monotonically increasing from As to Bi due to the increasing extension of the atomic wave function, although the lattice constant increases too. The degree of pinning of Sm 6th spin-up energy band to the Fermi level in and is similar to that obtained for the compound. An artificial shift via tuning of the hole level by changing by 6 eV is completely compensated by a charge transfer as small as 0.2 electron.
The most prominent difference in the electronic structure of the compound in comparison with the other two samarium pnictides is in the position and occupation of the 6th hole spin-up energy level. Figure 83(a) shows the expanded view of the total DOS of (X = As, Sb, or Bi) compounds. If one moves from to through the series, the peak position of the 6th hole spin-up level shifts toward higher energy from the Fermi level. The occupation of the 6th hole spin-up level reduces from 0.25 electrons in to 0.15 electrons in and to 0.01 electrons in . Therefore, the state is enhanced relative to the one in the series. This is consistent with the conclusion derived in [431] on the system. We should mention here that when we speak about partial occupation of the 6th hole level in compounds we imply that such an occupation is due to the hybridization effect between pnictide and Sm energy states.
The pnictides offer the unique opportunity to follow the evolution of intermediate valence as a function of composition. The driving force is the change of lattice constant upon exchanging the anion. In order to separate the influence of the lattice constant from the influence of the ionic potential of the pnictide component on the electronic structure of (X = As, Sb, and Bi), we present in Figure 83(b) the DOS of evaluated with the lattice constant of ( Å ) and for Å. The peak positions of the 6th hole spin-up level of with lattice parameter equal to that of the compound and real samarium antimonide are almost the same indicating the major role played by the lattice constant in this case. On the other hand, the occupation number of the 6th hole spin-up level in the compressed is 1.5 times larger than in compound. The reason is the larger Sm -pnictide hybridization in the former case due to larger extension of the atomic Bi wave function in comparison with the Sb one. It can be concluded that in the cases of the compounds the type of pnictide ion potential plays an essential role.
The results of the band structure calculations for and presented above were obtained with the assumption that the compounds contain three and one ions in the unit cell similar to . In this case it is still not clear why and show no trace of charge ordering at low temperatures. On the other hand, in earlier work, Ochiai et al. [427] suggested that and are typical dense Kondo systems with all four Sm ions being in the trivalent state. From the volume collapse in the high-pressure phase of , it was deduced that all Sm ions must be close to trivalency in this phase [426, 430].
The electronic structure of with trivalent Sm ions (not shown) differs significantly from the band structure with only one Sm ion in the trivalent state. In the former case As states are completely occupied and are far below the Fermi level. On the other hand, the previously empty Sm states become occupied due to charge transfer. A similar band structure was found also in with trivalent Sm ions.
Independently of the number of trivalent Sm ions the 6th hole level is always pinned at the Fermi energy. It makes the usual Kondo lattice scenario inappropriate for and because, for a Kondo resonance to develop, both the occupied and empty states must be sufficiently far away from the Fermi level.
In conclusion we note that the question of how many Sm ions are in the trivalent state in and compounds as well as in the high-pressure phase of (above 2.8 GPa) is still open. Analysis of the lattice constants suggests that all four Sm ions are probably in the trivalent state [426, 427]. On the other hand, the magnetic susceptibility at room temperature in is definitely larger than the theoretical value for , which can be explained by over 10% mixing of [427]. Moreover, high-resolution resonance photoemission spectra of have quite intensive components at 0 to 4 eV binding energy [5, 6], which indicates a significant amount of ions in the compound.
The principal question about the degree of Sm valency might be answered also by optical measurements. In Figure 84 we show the optical reflectivity and conductivity spectra of calculated in the LSDA+ approximation for different Sm valencies. The most prominent difference in the spectra is the extra peak between 0 and 1 eV in the optical conductivity with all four Sm ions in the trivalent state caused by interband transitions involving the occupied hybridized states. In with only one Sm ion being in the trivalent state Sm states are completely empty. As a result, the transitions involving the occupied states do not take place at small photon energies, and the erroneous peak structures around 0 to 1 eV disappear from the optical spectra. A small peak at around 0.15 eV presented in the optical conductivity spectrum with one Sm ion in the trivalent state is mostly determined by the interband transitions involving occupied states with predominantly As character to unoccupied states with predominantly Sm character situated in close vicinity of the Fermi level. Experimental measurements of the optical spectra in and are highly desired.
It should be mentioned that the experimental situation in differs from that, for example, in or in the sense that in the later systems a new generation of samples of much better quality became available during recent years, and more reliable data about transport properties, optical and photoemission spectra were obtained. In we still use old experimental data, and it is difficult to ascertain the full validity of measured properties based on the experiments of the early 1980s. The physical nature of the mixed-valence state in and compounds as well as in the high-pressure phase of requires further investigation theoretically as well as experimentally.
9.3. (X = As, Sb, and Bi)
Figure 85 shows the energy band structure and total density of states near the Fermi level for , , and calculated in the LSDA+U approximation [455]. For divalent ferromagnetic Eu ions seven spin-up energy bands per ion are fully occupied and hybridize with the bottom of the pnictide states (not shown). The other seven spin-down divalent Eu energy bands are situated far above the Fermi level at 7 to 7.5 eV and are hybridized with Eu states. The six bands are fully occupied and situated in the gap between the pnictide and states, while eight hole levels are completely unoccupied and cross the top of pnictide band and bottom of the Eu band. There is a hybridization energy gap of eV in which is formed between Bi and states.
(a)
(b)
(c)
The Fermi surface of consists of small closed hole pockets of Bi states centered at the Γ point and an electron ellipsoid of Eu states centered at the Z–b symmetry direction. There are no states at the Fermi level.
As in the case of the main trend in the electronic structure of the sequence of compounds (X = As, Sb, or Bi) results in a monotonic increase of the bandwidth going from As to Bi due to an increasing extension of the atomic wave function. Therefore, as one moves from to through the series, the unoccupied levels for nonmagnetic move from below toward the very top of the pnictide band. If is a semimetal, and are both semiconductors. The direct gap is equal to 0.41 eV and 0.12 eV and the indirect gap −0.26 eV and 0.02 eV in and , respectively. These gaps are between pnictide and Eu bands.
The temperature dependence of the Hall coefficient single crystal is presented in [429]. Large values of the Hall coefficient indicate a very low carrier concentration of this system. The same holds true for the electrical resistivity, which is, for instance, estimated as about 0.005 carriers/Eu ion at 200 K, assuming a one band model. Its positive sign suggests dominant hole conductivity in a wide temperature range. On the other hand, from our band structure calculations, is a semiconductor, although the calculated indirect gap is rather small in this system and any crystal imperfections or small doping can easily close the gap.
Among (X = As, Sb, and Bi) compounds only reveals the charge-ordering cubic-to-trigonal structural transformation. There is no information on the charge ordering for the other two compounds in the literature [456].
9.4.
The analysis on the site preference of and ions presented in [450] shows that ions do not occupy the sites within the error estimates. The ionic radii of and ions are 1.25 and 1.07 Å [457]. Larger ions prefer the slightly larger sites, although both sites are surrounded by eight sulfur atoms in the coordination of a distorted cube. The ordering scheme is that the ions occupy the sites, while both and ions occupy the sites in the ratio of 1 : 1. The chemical formula involving the information on the valence is given as . Two isomer shift peaks of the Mössbauer spectra of support the separation of and ions below K [458]. Since the observation temperature is higher than K, the gradual freezing of electron hopping occurs independently of the crystal-structural change, where the crystal still maintains the -type structure. The frequency of hopping can be described as a relaxation time to exchange the electrons in the observation of the Mössbauer spectra. Exponential temperature dependence of was reported with a continuous change through the phase transition. The values are , , , and sec at , 200, 250 and 325 K, respectively [458]. It should be noted that the hopping of electrons still exists at K even below the phase-transition temperature of K. Similar gradual freezing of electron hopping was observed in the neutron and X-ray Huang scattering of magnetite [124, 459].
Although the distribution of and ions at sites is random below K, the energy barrier to enable the electron hopping is relatively small even in the low-temperature phase so far examined. Therefore, a new charge ordering between and ions may exist for [450].
Figure 86 shows the partial density of states of for the low-temperature phase calculated in the LSDA+ approximation for eV [455]. In the LSDA+ band structure calculations of , it was assumed an additional charge ordering of the and ions in sublattice (see Figure 87) in a way which has been done in the case of the low-temperature charge-ordered magnetite in sublattice for and ions [10]. In contrast to LSDA, where the stable solution for is metallic, the LSDA+ method gave an insulator consistent with the experimental situation described in the introduction.
For divalent magnetic ions seven spin-down energy bands per ion are situated at the top of Eu states at 10 to 11 eV above Fermi level. The spin-up energy bands per ion are fully occupied and hybridized with about a half of the S band. There is a quasi-energy gap between hybridized and nonhybridized parts of S bands at −2.1 to −2.4 eV (Figure 86). Six nonmagnetic bands for both the and sites are fully occupied and situated in the gap between S and states, while eight hole levels are completely unoccupied and cross the very bottom of the Sm states at around 2 eV above the Fermi level (Figure 86). Both the occupied and empty Eu states are shifted downward at around 0.1 eV in comparison with the position of the states due to slightly different chemical bonding.
9.5.
The inhomogeneous mixed-valence state on the Sm sublattice was modeled by lowering the crystal symmetry in such a way that sites split into two groups consisting of 4 and 8 equivalent sites. The former were occupied by and the latter by ions.
In contrast to LSDA, where the charge-inhomogeneous solution for is metallic, the LSDA+ method gave an insulator. nonmagnetic bands are fully occupied and situated at the very top of S energy band (Figure 88). The hole levels are completely empty and well above the Fermi level hybridized with Sm states at around 9 eV (Figure 88). For trivalent Sm ions seven spin-down energy bands per ion are situated above Fermi level at 2.2 to 4.0 eV hybridized with Sm states. Five spin-up energy bands per ion are fully occupied and situated in the gap between S and energy bands (not shown). The other two empty spin-up energy bands are situated just above the Fermi level in the gap between occupied nonmagnetic bands and empty Sm bands (Figure 88).
Photoemission experiments, both X-ray (XPS) and ultraviolet, are of central importance for understanding mixed-valence materials (see the review of the early work by Campagna et al. [346]). In rare-earth photoemission, when the photon ejects an electron from the shell, it leaves behind a configuration; hence, the kinetic energy distribution curve of the emitted electron measures the spectra of the final-state hole. The final state has a characteristic multiplet splitting which serves as a fingerprint, and these are accurately resolved and calculable for rare-earth photoemission. By identifying the final-state hole the initial state can be inferred.
The partial DOS of the occupied part of the calculated in the LSDA+ approximations is compared with XPS measurements [314] in the top panel of Figure 89 [455]. The calculated DOS has been broadened to account for lifetime effects and for experimental resolution. The S states essentially do not contribute to the XPS spectra because of the low ionization cross-section compared with that of the Sm states [385]. Hence, the measurements only indicate the excitation energies relative to the Fermi level.
The theoretical DOS calculated using one-electron approximations cannot, of course, fully account for the multiplet splitting. Therefore, we present in the two other panels of Figure 89 the DOSs taking into account the multiplet structure of and ions. We used the final state multiplet structure presented in [370]. The multiplet structure for ion ( final state) consists of 3 terms , , and . The ion ( final state) has the multiplets , , , and . The relative intensities for the multiplet peaks were obtained on the basis of Cox calculations [387] using the fractional parentage method [388]. In this method Hund’s rule ground state is assumed for electrons, and then the coefficients of fractional parentage (Racah’s) for the configurations are calculated. The intensities for the various configurations (multiplets) are just the square of the coefficients of fractional parentage. In Figure 89 the XPS spectrum is modeled by a weighted sum of DOS curves. We aligned the centroid of the calculated occupied DOS peak with the centroid of the atomic final state multiplet and summed up the spectra scaling them according to the relative intensities of the multiplets. The agreement between LSDA+ theory and the XPS measurements is reasonably good. The disagreement in the intensity of some peaks might be explained by the influence of transition matrix elements which have not been included in the theoretical calculations. It is clear that the structures between −4.5 and −16 eV binding energy should be assigned to the final-state multiplet structure derived from five fully occupied spin-up bands and the structures between 0.0 and −4.5 eV are associated with the final-state multiplet structure of the divalent DOS. The LSDA calculations place energy bands in close vicinity of the Fermi level for both the and ions and hence are not able to produce the structures of the XPS spectrum in the −4.5 to −16 eV energy interval.
From the good agreement between theory and XPS measurements, we may conclude that the LSDA+ calculations give an accurate position for the occupied bands. The principal question is the energy position of the empty states, which is usually answered by optical or BIS measurements. In Figure 90 we show the experimental [439] real refractive index , extinction coefficient and optical reflectivity spectra of , as well as the spectra calculated with LSDA, LSDA+ and with the electrons in the core. This picture clearly demonstrates that the best description is unambiguously given by the LSDA+ approach. As was mentioned previously, the LSDA theory produces a metallic solution and, therefore, gives the wrong asymptotic behavior for the optical reflectivity and the extinction coefficient as → 0. The most prominent discrepancy in the LSDA spectra is the extra peaks between 0 and 1.5 eV in the extinction coefficient caused by interband transitions involving the occupied and unoccupied hybridized states. In the LSDA+ approach, the empty state energies are shifted upward due to the on-site Coulomb interaction . As a result, the transitions involving the unoccupied states do not take place at small photon energies, and the erroneous peak structures around 0 to 1.5 eV disappear from the optical spectra.
The calculations in which the electrons are treated as quasicore are able to reproduce correct asymptotic behavior for the optical reflectivity and the refractive index as → 0 similar to the LSDA+ calculations, but they fail in producing a peak at around 0.6 eV in the refractive index and the extinction coefficient . This peak is mostly determined by the interband transitions between occupied states hybridized with S states and two empty bands situated in close vicinity of the Fermi level.
9.6. Comparison between , and
Samarium chalcogenides (X = S, Se, Te) do not exhibit any evidence of charge-ordering at low temperature and show a charge-glass state due to the random distribution of and ions [445]. This glass transition of is in strong contrast with the charge ordering of the isomorphic compound . In the latter compound, a first-order charge-ordering transition occurs at about 188.5 K, below which the distribution of di- and trivalent cations is no longer random [450]. A microscopic description of the charge-ordering and the charge-glass states in rare-earth chalcogenides is completely lacking. Any detailed model calculations of these phenomena have to be based on the knowledge of their electronic and magnetic structures. In this section we compare and compounds in several aspects, namely, their band and magnetic structures, as well as the hybridization effects between the and S electrons.
One should mention that the magnetism of the (configuration 4) and (configuration ) ions is the reverse of that of the () and () ions; that is, the trivalent Eu ion has the same magnetic ground state of as that of the divalent Sm ion. The magnetic ground state of the ions is , no orbital moment.
Table 11 lists the calculated spin , orbital , and total magnetic moments (in ) of and . The spin and orbital moments are almost equal in and have opposite signs which gives a very small total magnetic moment of 0.5 per ion. Due to its atomic configuration, has no orbital moment.
Figure 91 shows the expanded view of the band structures and total DOS’s of and compounds. Both the compounds are semiconductors with an energy gap of 0.25 and 1.70 eV, respectively. The theoretically calculated energy gaps are in complete agreement with the optical measurements [439, 440]. The energy gap in is formed by the states at the sublattice positioned between occupied states which are strongly hybridized with S states and empty states which cut the very bottom of Eu band. The quite small energy gap in also separates the bands which belong to divalent and trivalent Sm ions, respectively. In both cases the gap depends on the position of the states, and the choice of can strongly affect its value; however, we should mention that in our calculations we did not consider the value of as an adjustable parameter but calculated it using the constrained LSDA approach [34].
(a)
(b)
Goto and Lüthi [7] argue that the difference between the charge glass state in (X = S, Se, or Te) and the charge ordering in could be the different hybridization effect of the electrons with electrons of the chalcogenides.
From the comparison of band structures presented in Figure 91, we can conclude that the hybridization effect is really quite different in and compounds. The S electrons hybridize with magnetic electrons in and nonmagnetic electrons in . Due to Zeeman splitting the magnetic states occupy quite a large energy interval inside of the S band, strongly hybridized with S states. Nonmagnetic states in cross the very top of S band; therefore, the – hybridization is expected to be smaller in comparison with the compound.
On the other hand, in and , nonmagnetic states are shifted downward from the top of chalcogen band. Taking into account that the extension of chalcogen valence wave function increases going from the top to the bottom of the band and also going from S to Te, one would expect that the – hybridization is increased going from to through the series. It manifests itself in a width of the states in these compounds. In Sm valence states are narrow with a high density of states. There is a hybridzation energy gap of about 0.2 eV between and S states. In the case of and the DOSs can hardly be distinguished from chalcogen DOSs and the hybridization in these compounds (not shown) is rather similar to the corresponding hybridization in than in . Nevertheless, as well as show no sign of a phase transition to charge ordering at low temperatures. In lowering the temperature the fluctuations of their electrons freeze gradually into a charge glass state similar to . Therefore, although the – hybridization effect is quite different in and compounds, it is probably not a main reason for the difference in their ground states.
Seeking the answer to the question why favors the charge glass state and does not exhibit charge ordering like , it was performed two numerical experiments. In the first one, by reducing the number of the symmetry operations all the atoms in the unit cell were made to be nonequivalent and then interchange the places of di- and trivalent Sm and Eu ions. It was found that the interchanging of Sm ions with different valency in costs smaller total energy than in the case of interchanging Eu ions in . So probably has a larger tendency to charge disorder in comparison with .
In the second experiment we tried to check whether the local easy magnetization axes for two nonequivalent pairs of magnetic ions in have the same orientation by calculating the total energy as a function of their magnetic moment direction. For simplicity electrons of nonmagnetic ion were placed in the core. In order to minimize the contribution of the exchange interaction into the total energy ions in each pair antiferromagnetically was arranged, thus making the exchange energy independent of the relative orientation of the magnetization of the pairs. It was found that the magnetic ions have different easy magnetization axes defined by the polar angles , and , , for the first and the second pairs, respectively ( and are defined with respect to the [001] direction). In order to verify these results we calculated the dependence of the total energy on the magnetization direction for each pair independently. This was achieved by putting the spin-orbit interaction strength at another pair of ions to zero, which effectively decouples their magnetic moments from the lattice. The total energy minima were again found for different magnetization directions, close to those mentioned above. It should be pointed out that strong magnetocrystalline anisotropy in prevents collinear magnetic order and may favor the charge glass state in this compound.
The chemical formula involving the information on the valence in is given as . There is only one type of magnetic ion in the unit cell of and two types of nonmagnetic ions. has no orbital magnetic moment (Table 11), and possesses a first-order nonmagnetic phase transition near K [447, 450], as well as phase transition to a ferromagnetic state below K [449]. However, a large difference between and indicates that the magnetic interactions probably play a minor role for the charge ordering in .
The difference in the magnetic structures and the hybridization effects in and play an important role in determining their ground states properties. However, it is still not clear why favors the charge glass state and does not exhibit charge ordering like . This question needs additional theoretical investigation using more sophisticated many-body approaches.
9.6.1. Summary
For , the LSDA+ band structure calculations provide a two-band model of the electronic structure: (1) a wide, nearly fully occupied Bi valence band and (2) a very narrow, marginally occupied Sm band, weakly hybridized with the Bi band in a small space region near the Γ point of the BZ. The mobility of heavy electrons is assumed to be negligible in comparison with the mobility of pnictide electrons. So the transport properties of are mostly determined by the number of pnictide holes. Pressure, doping, and so forth, may slightly change the relative position of these two bands and hence strongly affect the low carrier density and the transport properties. But the shell of the ions is little influenced as long as the charge order is maintained.
The most prominent difference in the electronic structure of the compound in comparison with the other two samarium pnictides is in the position and occupation of the 6th hole spin-up energy level. The pinning of a partly occupied 6th spin-up level is different in these compounds. If one moves from to , the peak position of the 6th hole spin-up level shifts toward higher energy from the Fermi level. The partial occupation of the 6th hole level is thus decreasing going from to along with a decrease of the lattice constant.
As classical mixed-valence compounds and (X = S, Se, or Te) constitute very interesting systems exhibiting unusual behavior due to strong electronic correlations. A detailed comparison between and shows that these two compounds have quite different electronic and magnetic structures as well as different hybridization character of the electrons with S electrons.
It was found that the – hybridization in is expected to be smaller in comparison with the compound. On the other hand, the – hybridization in and is closer rather to the corresponding hybridization in than in . Nevertheless, as well as shows no sign of a phase transition to a charge-ordered state at low temperatures. Therefore, the difference in the hybridization in and is probably not a main reason for the difference in their ground states.
and compounds have quite different magnetic structures. has no orbital moment. The orbital moment of magnetic ions in is quite large and has the opposite direction to the spin moment. It was found that easy magnetization axes are different for two nonequivalent ions, and the strong local magnetocrystalline anisotropy in might prevent the appearance of the collinear magnetic order in the compound.
In view of the distribution of valence ions, the low-temperature phase of is similar to the room-temperature phase of magnetite. Di- and trivalent ions are randomly distributed in the and sublattices in and , respectively. However, undergoes at K a first-order phase transition (Verwey transition) [9]. This phase transition is accompanied by long-range charge ordering of and ions on and sites of the sublattice. There are some indications that similar transitions with charge ordering of and on the sublattice may occur also in at low temperatures [450]. However, there are some serious technical difficulties in determining the crystal structure of below K [450].
10. YbMCu4 (M = Cu, Ag, Au, Pd, and In)
The YbMCu4 (M = Cu, Ag, Au, Pd, and In) compounds crystallize in the cubic AuBe5-type (C15) structure and preserve the Yb ion in its trivalent state with total angular momentum [460, 461]. These systems have been investigated extensively because of their rich variety of phenomena at low temperature. In particular, YbAgCu4 is known to show a typical dense Konde behaviour [461, 462], in which localized moments of () at high temperatures are gradually screened through the hybridization with the conduction electrons, resulting in the enhanced Pauli paramagnetic state down to very low temperatures. A moderately large electronic specific heat coefficient has also been reported as mJ/mol K2 [463]. Recently prepared by a high-pressure technique YbCu5 phase with C15 structure also shows Kondo-lattice formation [464] with an even larger electronic specific heat coefficient mJ/mol K2. Furthermore, the temperature dependence of magnetic susceptibility [461] and magnetic part of specific heat [462] in these systems are well described by the Bethe-ansatz solution of the Coqlin-Schrieffer model [465]. No magnetic ordering was found in both compounds down to 2.0 K [464, 466]. On the other hand, the Kondo effect is not dominant in YbAuCu4 and YbPdCu4, and long-range magnetic ordering is observed at 0.6 and 0.8 K, respectively [461]. Finally, YbInCu4 has attracted much attention recently because it is the only known stoichiometric compound that undergoes a first-order isostructural valence transition at ambient pressure [460, 467–469]. At high temperature Yb appears to be essentially trivalent, displaying Curie-Weiss susceptibility with a paramagnetic moment near free ion value of 4.5 . At the first-order valence transition at K, the Yb valence is reduced to approximately 2.8 (as estimated by X-ray-absorption and lattice constant measurements [467, 470]), with a consequent increase in lattice volume of 0.5% and a reduction in magnetic susceptibility and spin-disorder scattering [468]. High-resolution neutron powder-diffraction studies confirm that the first-order transition is an isostructural one, with YbInCu4 retaining its C15 structure at all temperatures [471, 472]. Such an “isomorphic” valence transition is fundamentally similar to the transition in cerium [473], which rises the question whether both transitions have a common origin.
The optical properties of the YbMCu4 (M = Ag, Au, Pd, and In) are investigated in [474]. In the case of YbInCu4 relevant differences in the optical spectrum were observed between 0.1 and 2 eV, above and below the transition temperature [474].
10.1. YbInCu4
The LSDA fully relativistic spin-polarized energy band structure and partial density of states (DOSs) of LuInCu4 are shown in Figure 92 [475]. The calculated energy band structure shows that LuInCu4 is a compensated semimetal with small carrier density which agrees well with electrical resistivity and Hall effect measurements [476]. The Fermi surface consists of two sheets. The 32nd band has closed hole sheets around W symmetry points, and the 33rd band has closed electron sheets around X points. The bands in the lowest region of the occupied part of the band structure of LuInCu4 between −9.5 and −7 eV have mostly In character with some amount of Cu and Lu characters mixed in. The highest region can be characterized as a bonding combination of Cu and In states. Cu bands are completely occupied and situated below the Fermi level at −4 to −1.5 eV. Lu states are almost empty and situated above the Fermi level.
In Figure 93 we compare the calculated complex dielectric function and the reflectivity with experiment [475]. As can be seen, theory in LSDA and experiment agree very well. Above 3 eV theory gives a slightly larger reflectivity in comparison with experimental measurements. One of the possible reasons for this is a nonideal sample surface, its roughness could reduce the optical reflectivity above 3 eV.
The LSDA total DOS of YbInCu4 is shown in Figure 94 [475]. The energy band structure of YbInCu4 is very similar to the LuInCu4 one. The bands in the lowest region have mostly In character with some amount of Cu and Yb characters mixed in. Cu bands are completely occupied and situated below the Fermi level between −4 and −1.5 eV. The large narrow peak close to the Fermi energy is formed by Yb states. Unoccupied bands of Yb are separated from the states by a quasigap, a characteristic and important feature of the YbInCu4 compound. The position of the LSDA states close to the Fermi energy is, on the other hand, in contradiction with the findings of XPS and BIS experiments [477].
The energy bands and partial density of states of YbInCu4 for eV are shown in Figures 95 and 96 [475]. For the trivalent Yb ion, thirteen electron bands are well below the Fermi level in the energy range between −6 and −8 eV (Figure 96). They are split due to spin-orbit coupling eV and separated from a hole state by the correlation energy . The unoccupied level, which through the Coulomb interaction is initially placed above , is pulled on during the process of self-consistent relaxation. A fundamental aspect of this observation is that we find the pinning of the state at to be a genetic property of YbInCu4 compound: it happens irrespective of the precise value of . The insensitiveness of this feature of the value, furthermore, can be understood as reflecting the large bandwidth of the In band with a low DOS and existing of a quasigap just above the Fermi level. The hole level should become partially occupied to achieve the required number of electrons within the Fermi sphere. Due to a small phase space for hybridization and small Yb -In orbital overlap, the DOS peak of the hole band is as narrow as 0.02 eV (Figure 97). It is now clear why the usual Kondo lattice scenario is inappropriate for this compound. For a Kondo resonance to develop both the occupied and empty states must be sufficiently far away from the Fermi level. Quite opposite to this situation the (almost) empty level is pinned to the Fermi energy. Since the upper level is only partly occupied, YbInCu4 is calculated to be an intermediate valent compound in agreement with the experimental data [460, 467–469].
(a)
(b)
(c)
After the consideration of the above band structure properties we turn to the optical spectra. In Figure 98 we show the LSDA and LSDA+ calculated and experimental optical spectra of YbInCu4 [475]. The best agreement between theory and the experiment was found to be when we used the LSDA+ approximation. The most prominent discrepancy in the LSDA spectra is the shifting of the prominent peak in the optical conductivity and imaginary part of dielectric function towards larger photon energies. This peak situated at ~1.2 eV in the experimentally measured optical spectra is mostly due to In → Yb interband transitions. These transitions take part between occupied and empty energy bands along L-W, X-W, and Γ-K symmetry directions and also in some inner parts of the Brillouin zone. Although states do not participate in the optical interband transitions in the energy interval from 0 to 5 eV (due to a large binding energy of occupied states and extremal narrowness of partly occupied hole level), they affect the optical spectra indirectly through changing of the ionicity of the Yb ion. LSDA produces the energy band structure of YbInCu4 with fully occupied bands for divalent Yb ions (Figure 94). The Coulomb repulsion strongly influences the electronic structure of YbInCu4. Thirteen occupied energy bands are well below the Fermi energy, and a hole 4 level is partly occupied and pinned at the Fermi level. Therefore, the ionicity of the Yb ion in the LSDA+ calculations is close to 3+. On the other hand, the electron density is closer to the nucleus than that of the , , and electrons. Hence, the increasing of the Yb ionicity (decreasing the number of electrons in the close vicinity of the nuclear) in the LSDA+ calculations leads to narrowing of Yb energy bands due to decreasing of nucleus screening. Therefore, empty Yb states in the LSDA+ calculations shift downwards decreasing the In → Yb interband energies and the prominent peak shifts to smaller energies in remarkable agreement with the experimental measurements (Figure 98).
(a)
(b)
The measurements of the optical spectra of YbInCu4 in [474] show that its optical response abruptly changes at the phase transition temperature (Figure 99), whereas no distortion of the crystal structure occurs. The major effect of such a phenomenon is also due to the changing of the Yb ionicity. As estimated by X-ray absorption and lattice constant measurements [467, 470] at the first-order valence transition at K, the Yb valence is reduced to approximately 2.8. In order to investigate the influence of the valence reduction of Yb ion, we performed the self-consistent LSDA+ calculations of the energy band structure and optical spectra of YbInCu4 using starting configuration of unoccupied 4 level equal to 0.9 and 0.8. Such a virtual crystal approximation [478] leads to the energy band structure with wider Yb energy bands due to increasing of the nuclear screening by electrons. The optical spectra, therefore, are shifted towards higher photon energies with good agreement with the experimental measurements (Figure 99).
(a)
(b)
The LSDA+ calculations show that the decreasing of Yb ionicity is accompanied by essential decreasing of the density of states at the Fermi level, which is equal to 17.0, 11.5, and 10.8 states/(unit cell eV) for , , and , respectively. This aspect reflects the fact that the ground state of YbInCu4 has the Yb valence less than 3+. We should mention here that for the configuration we mean the starting configuration with zero occupation of level. In the process of self-consistent relaxation initially empty hole level becomes partly occupied due to pinning at the Fermi level with occupation number equal to 0.14 (valence ). Using the configuration as initial configuration we achieved after the self-consistent calculations an occupation number equal to 0.24. These results are in a good agreement with X-ray absorption measurements at the Yb edge which gave and 2.8 above and below , respectively [467].
The total DOS at the Fermi level, resulting essentially from the hole states, yields for eV band structure contribution to the Sommerfeld constant of , 27, and 25.4 mJ for , , and , respectively in good agreement with specific heat measurements [467]. These measurements gave mJ at low temperatures below the phase transition. The specific heat is also abruptly increased at the phase transition temperature K [467].
10.2. YbMCu4 (M = Cu, Ag, Au, and Pd)
As an example, we show the LSDA+ energy bands of YbAgCu4 and YbCu5 for eV in Figures 100 and 101 [475]. The energy band structure of YbAgCu4 as well as YbCu5 compound is similar to YbInCu4 one (Figure 95). For the trivalent Yb ion, thirteen electron bands are well below the Fermi level in the energy range between −4.5 and −7 eV slightly shifted upwards in comparison with YbInCu4. They are split due to spin-orbit coupling eV and separated from the hole state by the correlation energy . The position of occupied bands in YbAgCu4 is in good agreement with X-ray photoemmission measurements. According to the XPS measurements the multiplet structure of the final states on sites is situated between −5 and −12 eV [477]. The most significant difference between the electronic structures of YbAgCu4 and YbInCu4 compounds is in the position of the hole level. In the case of YbInCu4 upper level is partly occupied and pinned at the Fermi level due to the existence of a quasigap in the density of states just above the Fermi level (Figure 95). In the YbAgCu4 occupied states shifted upward, a similar quasigap situated at 1.5 eV above the Fermi energy (Figure 100); therefore, a hole level in YbAgCu4 is completely empty and situated sufficiently far from the Fermi level (Figure 97). Such a situation is appropriate for the developing of the Kondo lattice scenario in this compound. The hole level has a similar position in YbCu5 (Figure 97), YbPdCu4 and YbAuCu4 compounds. YbCu5 is really a typical dense Kondo system with an electronic specific heat coefficient Γ = 550 mJ/mol [463], although, the Kondo effect is not dominant in YbAuCu4, and YbPdCu4, where a long-range magnetic ordering is observed at 0.6 and 0.8 K, respectively [461].
In Figures 102, 103 and 104 we show the LSDA+ calculated and experimentally measured optical spectra of YbAgCu4, YbPdCu4 and YbAuCu4 [475]. The agreement between the theory and the experiment is very good.
10.2.1. Summary
The optical spectra of YbMCu4 (M = Cu, Ag, Au, Pd, and In) are very sensitive tools for drawing conclusions about the appropriate model description. On account of the calculated optical spectra we conclude that YbInCu4 optical spectra are best described using the LSDA+ approach. It was found that the main peak in the optical conductivity of YbMCu4 at 1.2 eV results as In → Yb interband transitions between occupied and empty energy bands along L-W, X-W, and Γ-K symmetry directions and also in some inner parts of the Brillouin zone.
The measurements of the optical spectra of YbInCu4 show that its optical spectra between 0.1 and 2 eV significantly change at phase transition temperature. The theoretical calculations show that the major effect is due to the changing of the Yb ionicity. At the first-order valence transition at K, the Yb valence is reduced from 2.9 to approximately 2.8. This leads to the increase of the nuclear screening by electrons and increasing the In → Yb interband transition energies due to shifting of the empty Yb band upwards.
In YbInCu4 the upper hole level is partly occupied and pinned at the Fermi energy; therefore, YbInCu4 is calculated to be an intermediate valent compound in agreement with the experimental data. In the YbMCu4 (M = Cu, Ag, Au, and Pd) a hole level is completely empty and situated sufficiently far from the Fermi level. Such a situation is appropriate for the developing of the Kondo lattice scenario. YbCu5 and YbAgCu4 are really typical dense Kondo systems, although the Kondo effect is not dominant in YbAuCu4, and YbPdCu4, where a long-range magnetic ordering is observed. The different ground states observed in YbMCu4 (M = Cu, Ag, Au, and Pd) compounds result from the competition between three interactions: the crystal-field interaction, the magnetic intersite Ruderman-Kittel-Kasuya-Yosida interaction, and the intrasite Kondo effect. The evaluation of ground states of the compounds from first principles requires further investigation.
11. Conclusions
Almost localized electrons near the metal-insulator transitions are well described either by a simple itinerant picture in momentum space or by a localized picture in real space [2]. Theoretical and experimental efforts to make bridges between the itinerant and localized pictures have been made for years and have been fruitful [1]. However, this is still a challenging subject and many open questions have yet to be answered.
In this paper we present several examples of the first principle calculations of the electronic structure and various physical properties of transition metal oxides. The LSDA+ study of the low-temperature phases of and as well as show a charge- and orbitally ordered insulators below . The theoretically calculated energy gaps are in good agreement with the experimental values. It was shown that, while the screening of the charge disproportion is so effective that the total charge disproportion is rather small (0.23, 0.34, and 0.14 for the , , and , resp.), the charge order is well pronounced with an order parameter defined as the difference of occupancies of and sites in the and and and cations in the . This result demonstrates the utility of the LSDA+ method as an aide to experimental studies of CO structures.
From the results of LDA+ calculations performed for different models for the CO phase of -, it was found that the energy of the CO model with zig-zag ordering of ions is lower than the energy of the in-line CO model. The calculated effective exchange constants between magnetic moments are in good agreement with the experimental values determined from the high-temperature susceptibility.
Many spectroscopic properties such as the optical conductivity, dielectric functions, Kerr angle and Kerr ellipticity, X-ray absorption, and X-ray magnetic circular dichroism calculated from the energy bands and the LMTO eigenvectors in the LSDA+ approximation show an excellent agreement with derived from the experimental spectra in a wide energy range.
The global electronic structure of transition metal compounds on the eV scale is now well understood from spectroscopic and first-principles studies. The electronic structure parameters such as the on-site Coulomb energy , the charge-transfer energy, and exchange coupling constants have been deduced, and their systematic changes with chemical composition ranging from the Mott-Hubbard regime to the charge-transfer regime have been clarified [2]. The LSDA+ method provides a practical way to incorporate electron-electron interactions into first-principles band structure calculations. However, in many cases, the value has been determined not from first principles but empirically; that is, a true first-principles approach to strongly correlated systems is lacking so far. To understand the spectroscopic properties, effects of interactions that are not included in the standard models, namely, the long-range Coulomb interaction, electron-phonon interaction, impurity potentials, and so forth, need to be studied further in the future.
Marginally retained metals near the metal-insulator transition have offered interesting and rich phenomena for decades and will continue to do so in the future, presenting fundamental problems in condensed matter physics as well as potential sources of applications.
The Ce electrons in the CeFe2 hybridize strongly with the Fe electrons; therefore, calculations based on the density functional theory in the LSDA approach gave quite good description of the electronic structure and physical properties of CeFe2. A large magnetic moment at the Fe site induces spin splitting of the itinerant Ce and Ce states through exchange and hybridization effect. From the LSDA calculations, it has been deduced that the total moment is the result of the antiparallel coupling between Fe moment and cerium moment. This conclusion agrees well with the neutron diffraction, Compton scattering, and X-ray magnetic circular dichroism experiments. The XAS and XMCD spectra at the Ce edge reflect the energy distribution and the orbital character of the Ce band-like states. The LSDA calculations are able to provide a good agreement in the shape of the X-ray absorption spectra at the Ce edges with the experimental measurements.
On the other hand, the LSDA produces the stable metallic solution for Sm monochalcogenides at ambient pressure in contradiction with the experimental measurements. In this case the LSDA+ method gave correct insulator solution with energy gaps in good agreement with the experimental measurements. The Coulomb repulsion strongly influences the electronic structure of Sm monochalcogenides. For ions six bands are fully occupied and situated in the gap between chalcogen and Sm states. The hole levels are completely unoccupied and well above the Fermi level hybridized with Sm states. LSDA+ theory predicts that the samarium ion in these compounds is in an integer divalent state. It also shows a gradual decrease of the energy gap with reduction of the lattice constant. The LSDA+ theoretical calculations describe well the optical spectra of Sm monochalcogenides.
When applying external pressure to SmS and, hence, decreasing its lattice constant, the widths of Sm and bands are increased and the crystal-field splitting of the states is also increased. At a given pressure the band overlaps with the states. This leads to a first-order valence phase transition. The gap in SmS is closed at Å in good agreement with experimental measurements of SmS transport properties under pressure. For SmS with ions five bands are fully occupied and hybridize with chalcogenide states. The initially empty hole 6th level in the process of self-consistent relaxation becomes partly occupied with the DOS maximum situated in close vicinity of the Fermi level in the golden phase of SmS. The occupation number of the 6th hole level is equal to 0.45 (valence 2.55+) in a good agreement with the experimental estimates from spectroscopic methods and susceptibility measurements.
As classical mixed-valence narrow gap semiconductors SmB6 and YbB12 constitute very interesting systems exhibiting behavior due to strongly correlated electrons. The Coulomb repulsion strongly influences the electronic structure of SmB6. For ions eight hole levels are completely unoccupied and well above the Fermi level hybridized with Sm states. The bands are situated in close vicinity of the Fermi level. One of the levels is slightly unoccupied and extends just above the Fermi level around the X symmetry point, producing a noninteger Sm valency equal to 2.02+. There is a small hybridization gap at the Fermi level meV. The theoretically calculated energy gap is larger than the experimentally estimated one of around 3.6 to 5.2 meV determined from the activation energy and optical measurements. For five bands are fully occupied and situated at around 6 eV below the Fermi level. A 6th hole level is fully unoccupied and situated at about 0.34 eV above the Fermi level. The average positions of the occupied states in and calculations are in agreement with XPS measurements.
In the LSDA+ energy band structure calculations of the electronic structure of YbB12 with divalent Yb ions, all 14 bands are fully occupied and situated closely below the bottom of the Yb band. They are split due to spin-orbit coupling by eV. There is a small hybridization gap at the Fermi level. The theoretically calculated energy gap meV between Yb and Yb states is somewhat larger than the gap estimated from the activation energy and optical measurements and smaller than observed in tunneling experiments. For the trivalent Yb ion, thirteen electron bands are well below the Fermi level and hybridized with the B states. They are separated from a hole state by the correlation energy . The 14th unoccupied hole level is well above the Fermi level at around 1.5 eV.
The optical spectra of YbB12 can be considered as a mixture of two spectra coming from di- and trivalent ytterbium ions. Good agreement between theory and high-temperature optical reflectivity spectrum can be reached if one uses the sum of the optical reflectivity spectrum consisting of 20% ytterbium divalent and 80% ytterbium trivalent spectra. Low-temperature measurements show that below 20 K there is a gap development in the optical conductivity and reflectivity spectra of YbB12. The low-energy peak at 0.05 eV in the optical conductivity spectrum originates from the trivalent phase and can be explained as interband transitions between occupied and unoccupied Sm states along Γ-X and X-W symmetry directions. The prominent peak in the spectrum at around 0.4 eV is mostly derived from interband transitions between occupied Yb bands and empty Yb bands of the divalent phase in the vicinity of the W symmetry point as well as along the X-W symmetry direction.
In contrast to LSDA, where the stable solution for TmTe is a metal, the LSDA+ method gave an insulator with an indirect energy gap of 0.58 eV. LSDA+ theory predicts that the thulium ion in TmTe is in an integer divalent state. It also shows a gradual decreasing of the energy gap with reduction of the lattice constant. The gap is closed at Å in a good agreement with experimental measurements of TmTe transport properties under pressure and the compositionally induced semiconductor—metal transition in the system.
For the ions of TmS and TmSe twelve bands are fully occupied and hybridize with chalcogenide states. The 14th hole level is completely unoccupied and well above the Fermi level. The hole 13th level is partly occupied with DOS maximum situated in close vicinity of the Fermi level in TmS and TmSe. The degree of occupation and position of the partly occupied 13th level with respect to the Fermi level is different in TmS and TmSe. In TmS the hole level is almost empty and situated significantly far from the Fermi level. Such a situation is appropriate for achieving the Kondo lattice scenario. In TmSe the upper hole 13th level is pinned at the Fermi level, therefore, TmSe is expected to be an intermediate valent compound in agreement with experimental data. The occupation number of the 13th hole level is equal to 0.12 and 0.27 (valency 2.88+ and 2.73+) in TmS and TmSe, respectively, in a good agreement with the experimental estimates from lattice constant and XPS and UPS measurements.
The LSDA+ approach to band structure calculations of produce a band gap between the As band and the Yb band. As a consequence, a very narrow marginally occupied hole band is pinned close to the top of the As valence band via the charge balance between Yb and As which is governed by the large (~30 eV) bare Coulomb integral of the Yb state. The same charge balance pins the Fermi level close to the bottom of this hole band which has a width of 0.007 eV (80 K). It leads to an extremely low carrier density in . So for , the LSDA+ band structure calculations provide a two-band model of the electronic structure: (1) a wide, nearly fully occupied As valence band and (2) a very narrow, marginally occupied Yb band, very weakly hybridized with the As band in a small space region near the Γ point of the BZ. Pressure, doping and so forth. may slightly change the relative position of these two bands and hence strongly affected the low carrier density and the transport properties. But the shell of the ions is little influenced as long as the charge order is maintained. Similar situation was found to be also in the, where there is a wide, nearly fully occupied Bi valence band and a very narrow, marginally occupied Sm band, weakly hybridized with the Bi band in a small space region near the Γ point of the BZ.
As classical mixed-valence compounds and (X = S, Se, or Te) constitute very interesting systems exhibiting unusual behavior. A detailed comparison between and shows that these two compounds have quite different electronic and magnetic structures as well as different hybridization character of the electrons with S electrons.
The – hybridization in is expected to be smaller in comparison with the compound. On the other hand, the – hybridization in and is closer rather to the corresponding hybridization in than in . Nevertheless, as well as shows no sign of a phase transition to a charge ordered state at low temperatures. Therefore, the difference in the hybridization in and is probably not a main reason for the difference in their ground states.
and compounds have quite different magnetic structures. has no orbital moment. The orbital moment of magnetic ions in is quite large and has the opposite direction to the spin moment. It was found that easy magnetization axes are different for two nonequivalent ions, and the strong local magnetocrystalline anisotropy in might prevent the appearance of the collinear magnetic order in the compound.
In the view of the distribution of valence ions, the low-temperature phase of is similar to the room-temperature phase of magnetite. Di- and trivalent ions are randomly distributed in the and 8 sublattices in and , respectively. However, undergoes at K a first-order phase transition (Verwey transition) accompanying by long-range charge ordering of and ions on different sublattices. There are some indications that similar transitions with charge ordering of and on the 8 sublattice may occur also in at low temperatures [450].
The optical spectra of YbMCu4 (M = Cu, Ag, Au, Pd, and In) are very sensitive tools for drawing conclusions about the appropriate model description. On account of the calculated optical spectra, we conclude that YbInCu4 optical spectra are best described using the LSDA+ approach. It was found that the main peak in the optical conductivity of YbMCu4 at 1.2 eV results as In Yb interband transitions between occupied and empty energy bands along L-W, X-W, and Γ-K symmetry directions and also in some inner parts of the Brillouin zone. The measurements of the optical spectra of YbInCu4 show that its optical spectra between 0.1 and 2 eV significantly change at phase transition temperature. The theoretical calculations show that the major effect is due to the changing of the Yb valency. At the first-order valence transition at K the Yb valence is reduced from 2.9 to approximately 2.8. This leads to the increasing of the nuclear screening by electrons and increasing the In → Yb interband transition energies due to shifting of the empty Yb band upwards.
In YbInCu4 the upper hole level is partly occupied and pinned at the Fermi energy, therefore, YbInCu4 is calculated to be an intermediate valent compound in agreement with the experimental data. In the YbMCu4 (M = Cu, Ag, Au, and Pd) a hole level is completely empty and situated sufficiently far from the Fermi level. Such a situation is appropriate for the developing of the Kondo lattice scenario. YbCu5 and YbAgCu4 are really typical dense Kondo systems, although, the Kondo effect is not dominant in YbAuCu4 and YbPdCu4, where a long-range magnetic ordering is observed. The different ground states observed in YbMCu4 (M = Cu, Ag, Au, and Pd) compounds result from the competition between three interactions: the crystal field interaction, the magnetic intersite Ruderman-Kittel-Kasuya-Yosida interaction, and the intrasite Kondo effect. The evaluation of ground states of the compounds from first principles requires further investigation.
In conclusion we would like to point out that the LSDA+ method which combines LSDA with a basically static, that is, Hartree-Fock-like, mean-field approximation for a multiband Anderson lattice model does not contain true many-body physics. However, this method can be considered as the first step towards a better description of strongly correlated electron systems. The LSDA+ method provides a practical way to incorporate electron-electron interactions into first-principles band structure calculations. This method indeed makes better job in comparison with pure LSDA for most compounds.
The LSDA+ method gave a correct insulating ground state solution for Sm and Tm monochalcogenides, Sm and Yb borides as well as mixed-valent and charge-ordered Sm, Eu and Yb pnictides and chalcogenides and (R = Sm, Eu, Yb; X = As, Sb, Bi). This method is able to correctly describe many experimentally measured properties such as optical and magneto-optical spectroscopic measurements, X-ray photoemission and X-ray absorption, and bremsstrahlung isochromat spectroscopy measurements as well as X-ray magnetic circular dichroism.
However, the formation of the MV state in SmB6 and YbB12 clearly requires a treatment that goes beyond a static mean-field approximation and includes dynamical effects, for example, the frequency dependence of the self-energy. Similar is true also for the describing of the electronic structure of the charge glass state in , which is characterized by the random distribution of and ions in space. It is still unclear how well it performs in describing the mixed-valence state in golden SmS in the pressure range from 6 to 20 kbar. On one hand, we found the pinning of a partly occupied 6th level at the Fermi level, which is the typical situation for mixed-valence systems. On the other hand, LSDA+ calculations always produce a nonzero magnetic moment in the high-pressure phase of SmS, although all attempts to find any sign of magnetic ordering in this system gave no positive results for the last 30 years. It is more likely that our LSDA+ calculations describe well the situation in the metallic phase of SmS at pressure kbar with trivalent samarium ions.