The S1-S0 fluorescence excitation spectra of 5-chlorotropolone-M1 (M &#61; Kr, Xe, CH4) van der Waals (vdW) complexes in the region near the electronic origin have been measured in a supersonic free jet to investigate the effect of the vdW interactions on proton tunneling. Tunneling splittings have been observed in the vdW vibrations as well as in the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msubsup><mml:mtext>0</mml:mtext><mml:mtext>0</mml:mtext><mml:mtext>0</mml:mtext></mml:msubsup></mml:mrow></mml:math> transitions of the Kr and Xe complexes. The <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msubsup><mml:mtext>0</mml:mtext><mml:mtext>0</mml:mtext><mml:mtext>0</mml:mtext></mml:msubsup></mml:mrow></mml:math> tunneling splitting of the 5-chlorotropolone-(CH4)1 complex is significantly smaller than those of the Kr and Xe complexes. It has been suggested that the vdW vibrations couple with intramolecular motions, leading to a higher potential energy barrier to tunneling in the CH4 complex. The results of the 5- chlorotropolone complexes have been compared to those of the tropolone complexes.

Hiroshi  Sekiya

Taiji  Nakajima

Hidenori  Hamabe

Akira  Mori

Hitoshi  Takeshita

Yukio  Nishimura

Proton Tunneling In 5-Chlorotropolone-M1 (M = Kr, Xe, CH4) Van Der Waals Complexes

Systematic behavior of decay rates of resonances above dissociation threshold is investigated by using the theory of resonance scattering. The condition for the Rice-Ramsperger-Kassel-Marcus (RRKM) rate formula to be valid is clarified by analyzing the random model of unimolecular dissociation. The decay rate averaged over many resonances agrees with the RRKM rate when the mean spacing and the mean width of the resonance states coincide with each other. On the other hand, auto- and mutual-correlation functions of the non-stationary wave functions indicate a rather paradoxical and intriguing phenomenon: In the RRKM regime, insufficient time is left for intramolecular vibrational energy redistribution (IVR) before dissociation.

Kiyohiko  Someda

Hiroki  Nakamura

Frederick H. Mies

Competition Between Intramolecular Vibrational Energy Re-Distribution and Unimolecular Dissociation: A Scattering Theoretical Point of View

The resonance enhanced multiphoton ionization method has been applied to the study of NO-Ar van der Waals complex in the ns&#963; (n &#61; 3,4) Rydberg states. We have assigned the intermolecular vibrations appearing in the &#195;&#8212;<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mover accent="true"><mml:mtext>X</mml:mtext><mml:mo>&#x02DC;</mml:mo></mml:mover></mml:math> excitation spectrum of the complex. The bending structure appeared only with the excitation of the stretching mode in the &#195; state, which was interpreted by intermolecular forces. The <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mover accent="true"><mml:mtext>E</mml:mtext><mml:mo>&#x02DC;</mml:mo></mml:mover></mml:math>-&#195; excitation spectra were independent of the initial intermolecular level in the &#195; state and the dissociation threshold to NO(E2<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mo>&#x2211;</mml:mo><mml:mtext>+</mml:mtext></mml:msup></mml:mrow></mml:math>) &#43; Ar was determined to be 60950 cm-1. The s&#8211;d mixing in the 4s&#963; orbital would make the intermolecular vibrational structure in the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mover accent="true"><mml:mtext>E</mml:mtext><mml:mo>&#x02DC;</mml:mo></mml:mover></mml:math>&#8212;&#195;spectra complex.

Kazuhide  Tsuji

Kazuhiko  Shibuya

Kinichi  Obi

Intermolecular Vibrations of the Complex of NO in the ns&#963; Rydberg States and Ar

Excitation spectra and the Zeeman spectra of CS2 in the region of 31320-31445 cm-1were measured with sub-Doppler resolution. Observed rotational lines were classified to 14 series of lines (vibronic bands) and were named by the wavenumbers of their band origins. The 31344.9 band is the strongest one and is assigned as the main band of the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mi>V</mml:mi><mml:mn>1</mml:mn></mml:msup><mml:msub><mml:mi>B</mml:mi><mml:mn>2</mml:mn></mml:msub><mml:mn>0</mml:mn><mml:msub><mml:mi>v</mml:mi><mml:mrow><mml:mn>2</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>0<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:mi>K</mml:mi><mml:mo>=</mml:mo><mml:mn>0</mml:mn></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow></mml:math> &#8211; <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mi>X</mml:mi><mml:mn>1</mml:mn></mml:msup></mml:mrow></mml:math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msubsup><mml:mo>&#x2211;</mml:mo><mml:mi>g</mml:mi><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math> 0000 transition. Most of the extra bands may be allowed by the vibronic interaction between the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mi>V</mml:mi><mml:mn>1</mml:mn></mml:msup><mml:msub><mml:mi>B</mml:mi><mml:mn>2</mml:mn></mml:msub><mml:mn>0</mml:mn><mml:msub><mml:mi>v</mml:mi><mml:mrow><mml:mn>20</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:mi>K</mml:mi><mml:mo>=</mml:mo><mml:mn>0</mml:mn></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow></mml:math> level and singlet levels, which are mostly high vibrational levels of the 1<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mn>1</mml:mn></mml:msub></mml:mrow></mml:math>(<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mi>X</mml:mi><mml:mn>1</mml:mn></mml:msup></mml:mrow></mml:math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msubsup><mml:mo>&#x2211;</mml:mo><mml:mi>g</mml:mi><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math>) state. The Zeeman splittings are observed for several lines in almost all bands. These may be originating from the spin-orbit interaction between the rotational levels, which have accidentally nearly the same energy, of the 1<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mn>1</mml:mn></mml:msub></mml:mrow></mml:math>(<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mi>X</mml:mi><mml:mn>1</mml:mn></mml:msup></mml:mrow></mml:math><mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msubsup><mml:mo>&#x2211;</mml:mo><mml:mi>g</mml:mi><mml:mo>+</mml:mo></mml:msubsup></mml:mrow></mml:math>) state and the 3<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>A</mml:mi><mml:mn>2</mml:mn></mml:msub></mml:mrow></mml:math>(3<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mtext>&#x0394;</mml:mtext><mml:mi>u</mml:mi></mml:msub></mml:mrow></mml:math>) or/and 3<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>B</mml:mi><mml:mn>2</mml:mn></mml:msub></mml:mrow></mml:math>(3<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mtext>&#x0394;</mml:mtext><mml:mi>u</mml:mi></mml:msub></mml:mrow></mml:math>) state.

Atsushi  Doi

Masaya  Ohtsuka

Kiyoshi  Nishizawa

Masaaki  Baba

Hajime  Kat&#244;

Sub-Doppler High-Resolution Spectroscopy of 15V Band of CS2 and the Zeeman Effect

Kaoru  Yamanouchi

Preface to the Spesial Issue in Honor of Professor Soji Tsuchiya

The vibrational structure was recorded for the S1 (<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mi>&#x03C0;</mml:mi></mml:math>* - n) state of acetaldehyde (CH3CHO) and itsdeuterated derivatives (CH3CDO, CD3CHO and CD3CDO up to &#8764;3500 cm-1above the 0-0 bands withthe LIF (laser induced fluorescence) and PHOFEX (photofragment excitation) techniques. In thePHOFEX spectroscopy, the yield of the formyl radical, HCO(<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mover accent="true"><mml:mtext>X </mml:mtext><mml:mo>&#x02DC;</mml:mo></mml:mover></mml:math>) or DCO(<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mover accent="true"><mml:mtext>X </mml:mtext><mml:mo>&#x02DC;</mml:mo></mml:mover></mml:math>), produced in the photodissociationof acetaldehyde is measured against the excitation frequency. The yield was determined bymonitoring one of the rotational lines in the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mover accent="true"><mml:mtext>B</mml:mtext><mml:mo>&#x02DC;</mml:mo></mml:mover></mml:math> &#8592; <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mover accent="true"><mml:mtext>X</mml:mtext><mml:mo>&#x02DC;</mml:mo></mml:mover></mml:math> transition of the formyl radical by the LIF technique. This is the first measurement of the vibronic structure of acetaldehydes in supersonic jets above the dissociation threshold where they are non-fluorescent. The results have made it possible to locate <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>v</mml:mi><mml:mn>4</mml:mn></mml:msub></mml:mrow></mml:math> (the C&#61;O stretching) and <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mn>2</mml:mn><mml:msub><mml:mi>v</mml:mi><mml:mn>4</mml:mn></mml:msub></mml:mrow></mml:math> bands unequivocally; the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>v</mml:mi><mml:mn>4</mml:mn></mml:msub></mml:mrow></mml:math> fundamentals at 1217, 1189, 1210 and 1178 cm-1 above the 0-0 band for CH3CHO, CH3CDO, CD3CHO and CD3CDO, respectively. The correspondingovertone (<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mn>2</mml:mn><mml:msub><mml:mi>v</mml:mi><mml:mn>4</mml:mn></mml:msub></mml:mrow></mml:math>)bands are observed, respectively, at 2414, 2350, 2399 and 2334cm-1. All the vibronicbands newly observed in the PHOFEX spectra are found to be interpreted as the combinations of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>v</mml:mi><mml:mn>4</mml:mn></mml:msub></mml:mrow></mml:math> and<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mn>2</mml:mn><mml:msub><mml:mi>v</mml:mi><mml:mn>4</mml:mn></mml:msub></mml:mrow></mml:math>with the modes appearing in the lower frequency (&#60; 1200 cm-1) region, which consist of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>v</mml:mi><mml:mrow><mml:mn>10</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>(theC&#8212;C&#8212;O in-plane bending), <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>v</mml:mi><mml:mrow><mml:mn>14</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math> (the C&#61;O out-of-plane wagging) and <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mi>v</mml:mi><mml:mrow><mml:mn>15</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math> (the methyl torsion).

Takumi  Kono

Masao  Takayanagi

Ichiro  Hanazaki

The C&#x3D;O Stretching Frequency in the S1 (<svg style="vertical-align:-0.1638pt" height="8.1499996" version="1.1" viewBox="0 0 10.175 8.1499996" width="10.175" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg"><g transform="matrix(.017,-0,0,-.017,.062,7.888)"><path id="x1D70B" d="M574 449q-23 -58 -38 -79q-16 -4 -79 -4q-27 -100 -46 -219q-14 -87 7 -87t74 36l13 -27q-74 -81 -139 -81q-48 0 -48 62q0 22 8 59l60 258l-154 4q-21 -103 -54.5 -209t-64.5 -151q-38 -23 -83 -23l-7 15q46 36 94 152.5t64 216.5q-81 0 -138 -54l-18 23q22 27 39.5 43&#xA;t61.5 33.5t100 17.5q43 0 131.5 -2.5t129.5 -2.5q23 0 33.5 5t24.5 25z" /></g></svg>*- n) State of Acetaldehyde and its Deuterated Derivatives Determined With the Photofragment Excitation Spectroscopy

Reaction kinetics of ground, Ti(a3F) and V(a4F), and excited, Ti(a5F) and V(a6D), states atoms with some simple molecules have been studied by a discharge-flow tube technique. Laser-induced fluorescence (LIF) was used to determine the concentration of the metal atoms as a function of the flow rate of the reactant molecule to obtain effective bimolecular rate constants. The rate constants of reactions with OX (X &#61; O, N, N2) and H2S show strong inverse correlation with effective ionization potentials (I.P.-Eel, where I.P. and Eel are ionization potential and electronic energy of metal atom) of the metal atoms. This result suggests that the electron transfer mechanism plays an important role in these reactions. The large rate constants for electronic excited states can be explained by the crossing between ionic and flat neutral potential energy surfaces. The inefficient reaction rates measured for ground states can be explained by the repulsive nature of 4s2 configuration which can result in a potential barrier.

Kenji  Honma

David E. Clemmer

The Importance of Electron Transfer Mechanism in Reactions of Neutral Transition Metal Atoms

The reactions of Zn(41P1) with H2 and D2 were studied by employing a laser pump-and-probe technique. The nascent vibrational state distributions of ZnH(X 2<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mo>&#x2211;</mml:mo><mml:mo>+</mml:mo></mml:msup></mml:mrow></mml:math>) and ZnD(X 2<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mo>&#x2211;</mml:mo><mml:mo>+</mml:mo></mml:msup></mml:mrow></mml:math>) were determined. The distributions were much cooler than the statistically expected ones. These results are consistent with the insertive attack model proposed for other excited metal-H2 systems. The quantum yield for the production of ZnH(X 2<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msup><mml:mo>&#x2211;</mml:mo><mml:mo>+</mml:mo></mml:msup></mml:mrow></mml:math>) was measured to be low; around 0.5 of that for cn4. Three-body dissociation processes to produce Zn(41S0) &#43; H &#43; H must be more dominant than the production of ZnH.

Hironobu  Umemoto

Masamichi  Tsunashima

Shigeru  Tsunashima

Hiroyuki  Ikeda

Nascent Vibrational State Distributions of ZnH(X 2
 <svg style="vertical-align:-3.11897pt" height="18.112499" version="1.1" viewBox="0 0 20.475 18.112499" width="20.475" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg"><g transform="matrix(.017,-0,0,-.017,.062,14.175)"><path id="x2211" d="M697 -46l-42 -182h-602v25l325 457l-308 460v25h585l12 -154l-28 -5q-17 63 -39 88q-12 15 -36.5 20.5t-80.5 5.5h-277l268 -396l-311 -440h382q51 0 75.5 19.5t47.5 83.5z" /></g><g transform="matrix(.012,-0,0,-.012,12.812,5.887)"><path id="x2B" d="M535 230h-212v-233h-58v233h-213v50h213v210h58v-210h212v-50z" /></g></svg>) and ZnD(X 2
 <svg style="vertical-align:-3.11897pt" height="18.112499" version="1.1" viewBox="0 0 20.475 18.112499" width="20.475" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns="http://www.w3.org/2000/svg"><g transform="matrix(.017,-0,0,-.017,.062,14.175)"><use xlink:href="#x2211"/></g><g transform="matrix(.012,-0,0,-.012,12.812,5.887)"><use xlink:href="#x2B"/></g></svg>) Produced in the Reactions of Zn(41P1) With H2 and D2

Negative-ion photoelectron spectroscopy has been applied in order to obtain size dependent informationabout the electronic structure of clusters of metal atoms solvated with polar molecules. In the presentpaper we have investigated the photoelectron spectra of Cu2-<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:msub><mml:mtext>H</mml:mtext><mml:mtext>2</mml:mtext></mml:msub><mml:mtext>O</mml:mtext></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow><mml:mi>n</mml:mi></mml:msub></mml:mrow></mml:math>, cluster ions with 2 &#61; 0&#8211;4 and alsothose of Cu2-<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:msub><mml:mtext>H</mml:mtext><mml:mtext>2</mml:mtext></mml:msub><mml:mtext>O</mml:mtext></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow><mml:mi>n</mml:mi></mml:msub></mml:mrow></mml:math>, with n &#61; 0 and 1. In the spectra of Cu2-<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:msub><mml:mtext>H</mml:mtext><mml:mtext>2</mml:mtext></mml:msub><mml:mtext>O</mml:mtext></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow><mml:mi>n</mml:mi></mml:msub></mml:mrow></mml:math>, the lowest energy bands were assignedto the electron detachment from the CuOH-<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:msub><mml:mtext>H</mml:mtext><mml:mtext>2</mml:mtext></mml:msub><mml:mtext>O</mml:mtext></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow><mml:mrow><mml:mi>n</mml:mi><mml:mo>&#x2212;</mml:mo><mml:mn>1</mml:mn></mml:mrow></mml:msub></mml:mrow></mml:math>, which were produced in the source together withthe above cluster ions. The observed bands for Cu2-<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mrow><mml:mrow><mml:mo>(</mml:mo><mml:mrow><mml:msub><mml:mtext>H</mml:mtext><mml:mtext>2</mml:mtext></mml:msub><mml:mtext>O</mml:mtext></mml:mrow><mml:mo>)</mml:mo></mml:mrow></mml:mrow><mml:mi>n</mml:mi></mml:msub></mml:mrow></mml:math> were all assigned to the transitions to thestates originating in the ground 2S and first excited 2D states of the Cu atom. The stepwise hydration for Cu- and <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:msub><mml:mrow><mml:mtext>Cu</mml:mtext></mml:mrow><mml:mtext>2</mml:mtext></mml:msub></mml:mrow></mml:math>- was discussed from the observed spectral shifts.

Fuminori  Misaizu

Keizo  Tsukamato

Masaomi  Sanekata

Kiyokazu  Fuke

Photoelectron Spectroscopy of Mass-Selected Copper-Water Cluster Negative Ions

The CH(X2II) radical beam was produced via the decomposition of methanol by a dc-discharge in a pulsed supersonic beam. The CH radical beam was rotationally state-selected and separated from other discharge products by using an electrostatic hexapole field. The chemiluminescence from the reaction of CH in the &#124;3/2, 3/2, 3/2&#62; state with NO was measured under the crossed beam condition. The wavelength region of the present chemiluminescence confirms no NH(A3II) formation. The formation of HCN(X) and/or OH(X2II) is tentatively proposed.

M.  Takezaki

H.  Ohoyama

T.  Kasai

K.  Kuwata

Formation of the State-Selected CH Radical Beam and its Application to The CH &#43; NO Reaction

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