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Advances in Physical Chemistry

Volume 2012 (2012), Article ID 236750, 12 pages

http://dx.doi.org/10.1155/2012/236750

Research Article

## New *ab Initio* Potential Energy Surfaces for the Renner-Teller Coupled
and
States of CH_{2}

^{1}Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China^{2}Key Laboratory of Luminescence and Optical Information, Ministry of Education, Institute of Optoelectronic Technology, Beijing Jiaotong University, Beijing 100044, China

Received 31 August 2011; Revised 31 October 2011; Accepted 9 November 2011

Academic Editor: António Varandas

Copyright © 2012 Haitao Ma et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

#### Linked References

- R. A. Beärda, M. C. Van Hemert, and E. F. Van Dishoeck, “Photodissociation of CH
_{2}. I. Potential energy surfaces of the dissociation into CH and H,”*The Journal of Chemical Physics*, vol. 97, no. 11, pp. 8240–8249, 1992. - G. Herzberg and J. W. C. Johns, “The Spectrum and Structure of Singlet CH
_{2},”*Proceedings of the Royal Society of London A*, vol. 295, no. 1441, pp. 107–128, 1966. - A. Kalemos, T. H. Dunning, A. Mavridis, and J. F. Harrison, “CH
_{2}revisited,”*Canadian Journal of Chemistry*, vol. 82, no. 6, pp. 684–693, 2004. View at Publisher · View at Google Scholar · View at Scopus - C. D. Sherrill, M. L. Leininger, T. J. V. Huis, and H. F. Schaefer III, “Structures and vibrational frequencies in the full configuration interaction limit: predictions for four electronic states of methylene using a triple-zeta plus double polarization (TZ2P) basis,”
*The Journal of Chemical Physics*, vol. 108, no. 3, pp. 1040–1049, 1998. View at Scopus - M. N. R. Ashfold, M. A. Fullstone, G. Hancock, and G. Duxbury, “Laser induced fluorescence spectroscopy of the CD
_{2}($\stackrel{\u0303}{\mathrm{a}}$${}^{1}{A}_{1}$) radical: Renner-teller effect in CH_{2 }and CD_{2},”*Molecular Physics*, vol. 45, no. 4, pp. 887–896, 1982. - W. Xie, C. Harkin, H. L. Dai, W. H. Green, Q. K. Zheng, and A. J. Mahoney, “Transient vibrational spectroscopy of $\stackrel{\u0303}{\mathrm{a}}$${}^{1}{A}_{1}$ CH
_{2}v_{2}= 2,”*Journal of Molecular Spectroscopy*, vol. 138, no. 2, pp. 596–601, 1989. View at Scopus - W. Xie, C. Harkin, and H. L. Dai, “Bending overtones and barrier height of $\stackrel{\u0303}{\mathrm{a}}$${}^{1}{A}_{1}$ CH
_{2}by flash photolysis stimulated emission pumping,”*The Journal of Chemical Physics*, vol. 93, no. 7, pp. 4615–4623, 1990. View at Scopus - G. V. Hartland, D. Qin, and H. L. Dai, “Renner-Teller effect on the highly excited bending levels of $\stackrel{\u0303}{\mathrm{a}}$${}^{1}{A}_{1}$ CH
_{2},”*The Journal of Chemical Physics*, vol. 102, no. 17, pp. 6641–6645, 1995. View at Scopus - B. C. Chang, M. Wu, G. E. Hall, and T. J. Sears, “Near-infrared vibronic spectrum of the CH
_{2}$\stackrel{\u0303}{\mathrm{b}}$${}^{1}{B}_{1}$*←*$\stackrel{\u0303}{\mathrm{a}}$${}^{1}{A}_{1}$ transition,”*The Journal of Chemical Physics*, vol. 101, no. 11, pp. 9236–9245, 1994. View at Scopus - K. Kobayashi, L. D. Pride, and T. J. Sears, “Absorption spectroscopy of singlet CH
_{2}near 9500 ${\mathrm{c}\mathrm{m}}^{-1}$,”*The Journal of Physical Chemistry A*, vol. 104, no. 45, pp. 10119–10124, 2000. View at Scopus - H. Petek, D. J. Nesbitt, D. C. Darwin, P. R. Ogilby, C. B. Moore, and D. A. Ramsay, “Analysis of CH
_{2}$\stackrel{\u0303}{\mathrm{a}}$${}^{1}{A}_{1}$ (1,0,0) and (0,0,1) Coriolis-coupled states, $\stackrel{\u0303}{\mathrm{a}}$${}^{1}{A}_{1}$-$\stackrel{\u0303}{\mathrm{x}}$${}^{3}{B}_{1}$ spin-orbit coupling, and the equilibrium structure of CH_{2}$\stackrel{\u0303}{\mathrm{a}}$${}^{1}{A}_{1}$,”*The Journal of Chemical Physics*, vol. 91, no. 11, pp. 6566–6578, 1989. View at Scopus - G. E. Hall, A. V. Komissarov, and T. J. Sears, “Doppler-resolved spectroscopy as an assignment tool in the spectrum of singlet methylene,”
*The Journal of Physical Chemistry A*, vol. 108, no. 39, pp. 7922–7927, 2004. View at Publisher · View at Google Scholar · View at Scopus - A. J. Marr, T. J. Sears, and B. C. Chang, “Near-infrared spectroscopy of CH
_{2}by frequency modulated diode laser absorption,”*The Journal of Chemical Physics*, vol. 109, no. 9, pp. 3431–3442, 1998. View at Publisher · View at Google Scholar · View at Scopus - Z. Wang, Y. Kim, G. E. Hall, and T. J. Sears, “State mixing and predissociation in the $\stackrel{\u0303}{\mathrm{c}}$
*←*$\stackrel{\u0303}{\mathrm{a}}$ band system of singlet methylene studied by optical-optical double resonance,”*The Journal of Physical Chemistry A*, vol. 112, no. 39, pp. 9248–9254, 2008. View at Publisher · View at Google Scholar · View at Scopus - K. Kobayashi, G. E. Hall, and T. J. Sears, “The spectrum of CH
_{2}near 1.36 and 0.92*μ*m: reevaluation of rotational level structure and perturbations in $\stackrel{\u0303}{\mathrm{a}}$(010),”*The Journal of Chemical Physics*, vol. 124, no. 18, Article ID 184320, 2006. View at Publisher · View at Google Scholar · View at Scopus - C. -H. Chang, Z. Wang, G. E. Hall, T. J. Sears, and J. Xin, “Transient laser absorption spectroscopy of CH
_{2}near 780 nm,”*Journal of Molecular Spectroscopy*, vol. 267, no. 1-2, pp. 50–57, 2011. View at Publisher · View at Google Scholar - W. H. Green Jr., N. C. Handy, P. J. Knowles, and S. Carter, “Theoretical assignment of the visible spectrum of singlet methylene,”
*The Journal of Chemical Physics*, vol. 94, no. 1, pp. 118–132, 1991. View at Scopus - G. Duxbury, A. Alijah, B. D. McDonald, and C. Jungen, “Stretch-bender calculations of the effects of orbital angular momentum and vibrational resonances in the spectrum of singlet methylene,”
*The Journal of Chemical Physics*, vol. 108, no. 6, pp. 2351–2360, 1998. View at Scopus - J. P. Gu, G. Hirsch, R. J. Buenker et al., “A theoretical study of the absorption spectrum of singlet CH
_{2},”*Journal of Molecular Structure*, vol. 517-518, pp. 247–264, 2000. View at Publisher · View at Google Scholar · View at Scopus - R. Renner, “Zur Theorie der Wechselwirkung zwischen Elektronen- und Kernbewegung bei dreiatomigen, stabförmigen Molekülen,”
*Zeitschrift für Physik*, vol. 92, no. 3-4, pp. 172–193, 1934. View at Publisher · View at Google Scholar · View at Scopus - G. J. Halasz, A. Vibok, R. Baer, and M. Baer, “Renner-Teller nonadiabatic coupling terms: an
*ab-initio*study of the HNH molecule,”*The Journal of Chemical Physics*, vol. 124, no. 8, Article ID 081106, 4 pages, 2006. - G. J. Halász, Á. Vibók, R. Baer, and M. Baer, “D matrix analysis of the Renner-Teller effect: an accurate three-state diabatization for NH
_{2},”*The Journal of Chemical Physics*, vol. 125, no. 9, Article ID 094102, 9 pages, 2006. View at Publisher · View at Google Scholar - S. Zhou, Z. Li, D. Xie, S. Y. Lin, and H. Guo, “An
*ab initio*global potential-energy surface for NH_{2}(*A*^{2}*A*′) and vibrational spectrum of the Renner-Teller*A*^{2}*A*′-*X*^{2}*A*′′ system,”*The Journal of Chemical Physics*, vol. 130, no. 18, Article ID 184307, 10 pages, 2009. View at Publisher · View at Google Scholar - G. Duxbury, B. D. McDonald, M. Van Gogh, A. Alijah, C. Jungen, and H. Palivan, “The effects of vibrational resonances on Renner-Teller coupling in triatomic molecules: the stretch-bender approach,”
*The Journal of Chemical Physics*, vol. 108, no. 6, pp. 2336–2350, 1998. View at Scopus - C. Jungen, D. N. Malm, and A. J. Merer, “Analysis of a ${}^{1}{\u2206}_{u}{{-}^{1}{\mathrm{\Sigma}}_{\mathrm{g}}}^{+}$ transition of CS
_{2}in the near ultraviolet,”*Canadian Journal of Physics*, vol. 51, no. 14, pp. 1471–1490, 1973. - B. Ostojić, “The dissociation of singlet methylene,”
*Journal of Molecular Spectroscopy*, vol. 212, no. 1, pp. 130–131, 2002. View at Publisher · View at Google Scholar · View at Scopus - B. Bussery-Honvault, P. Honvault, and J. M. Launay, “A study of the ${\mathrm{C}(}^{1}D)+{\mathrm{H}}_{2}$→$\mathrm{C}\mathrm{H}+\mathrm{H}$ reaction: global potential energy surface and quantum dynamics,”
*The Journal of Chemical Physics*, vol. 115, no. 23, pp. 10701–10708, 2001. View at Publisher · View at Google Scholar · View at Scopus - L. Bañares, F. J. Aoiz, P. Honvault, B. Bussery-Honvault, and J. M. Launay, “Quantum mechanical and quasi-classical trajectory study of the ${\mathrm{C}(}^{1}D)+{\mathrm{H}}_{2}$ reaction dynamics,”
*The Journal of Chemical Physics*, vol. 118, no. 2, pp. 565–568, 2003. View at Publisher · View at Google Scholar · View at Scopus - B. Bussery-Honvault, J. Julien, P. Honvault, and J.-M. Launay, “Global 1 1A
*″*potential energy surface of CH_{2}and quantum dynamics of a sideways insertion mechanism for the ${\mathrm{C}(}^{1}D)+{\mathrm{H}}_{2}$ → ${\mathrm{C}\mathrm{H}(}^{2}\mathrm{\Pi})+\mathrm{H}$ reaction,”*Physical Chemistry Chemical Physics*, vol. 7, no. 7, pp. 1476–1481, 2005. View at Publisher · View at Google Scholar · View at Scopus - S. Joseph and J. C. Varandas, “Accurate double many-body expansion potential energy surface for the lowest singlet state of methylene,”
*The Journal of Physical Chemistry A*, vol. 113, no. 16, pp. 4175–4183, 2009. View at Publisher · View at Google Scholar - A. J. C. Varandas, “Intermolecular and intramolecular potentials: topographical aspects, calculation, and functional representation via a double many-body expansion method,”
*Advances in Chemical Physics*, vol. 74, pp. 255–338, 1988. - S. Joseph, P. J. S. B. Caridade, and A. J. C. Varandas, “Quasiclassical trajectory study of the ${\mathrm{C}(}^{1}D)+{\mathrm{H}}_{2}$ reaction and isotopomeric variants: kinetic isotope effect and cd/ch branching ratio,”
*The Journal of Physical Chemistry A*, vol. 115, no. 27, pp. 7882–7890, 2011. View at Publisher · View at Google Scholar - R. Dawes, A. F. Wagner, and D. L. Thompson, “Ab initio wavenumber accurate spectroscopy: ${}^{1}{\text{C}\text{H}}_{2}$ and HCN vibrational levels on automatically generated IMLS potential energy surfaces,”
*The Journal of Physical Chemistry A*, vol. 113, no. 16, pp. 4709–4721, 2009. View at Publisher · View at Google Scholar · View at Scopus - X. Liu, W. Bian, X. Zhao, and X. Tao, “Potential energy surface intersections in the $\text{C}{(}^{1}D){\text{H}}_{2}$ reactive system,”
*The Journal of Chemical Physics*, vol. 125, Article ID 074306, 7 pages, 2006. View at Publisher · View at Google Scholar - H. Zhao, W. Bian, and K. Liu, “A theoretical study of the reaction of O(
^{3}P) with isobutene,”*Journal of Physical Chemistry A*, vol. 110, no. 25, pp. 7858–7866, 2006. View at Publisher · View at Google Scholar - N. Matsunaga and D. R. Yarkony, “Energies and derivative couplings in the vicinity of a conical intersection. II. CH
_{2}(2^{3}*A*^{′′,3}3^{3}*A*′′) and H_{2}S(${1}^{1}$*A*′′${2}^{1}$*A*′′), unexpected results in an ostensibly standard case,”*The Journal of Chemical Physics*, vol. 107, no. 19, pp. 7825–7838, 1997. View at Scopus - D. R. Yarkony, “Diabolical conical intersections,”
*Reviews of Modern Physics*, vol. 68, no. 4, pp. 985–1013, 1996. View at Publisher · View at Google Scholar · View at Scopus - J. Ivanic, G. J. Atchity, and K. Ruedenberg, “Violation of the weak noncrossing rule between totally symmetric closed-shell states in the valence-isoelectronic series O
_{3}, S_{3}, SO_{2}, and S_{2}O,”*The Journal of Chemical Physics*, vol. 107, no. 11, pp. 4307–4317, 1997. View at Scopus - G. J. Atchity and K. Ruedenberg, “Strong shifts in diabatic nondynamic electron correlations cause conical intersection between low-lying closed-shell adiabatic singlets of like symmetry in ozone,”
*The Journal of Chemical Physics*, vol. 99, no. 5, pp. 3790–3798, 1993. View at Scopus - H. Ma, X. Liu, W. Bian, L. Meng, and S. Zheng, “A theoretical study of the mechanism and kinetics of $\mathrm{F}+{\mathrm{N}}_{3}$ reactions,”
*ChemPhysChem*, vol. 7, no. 8, pp. 1786–1794, 2006. View at Publisher · View at Google Scholar · View at Scopus - P. Jensen, M. Brumm, W. P. Kraemer, and P. R. Bunker, “A treatment of the Renner effect using the MORBID hamiltonian,”
*Journal of Molecular Spectroscopy*, vol. 171, no. 1, pp. 31–57, 1995. View at Publisher · View at Google Scholar · View at Scopus - K. A. Peterson and T. H. Dunning, “Accurate correlation consistent basis sets for molecular core-valence correlation effects: the second row atoms Al-Ar, and the first row atoms B-Ne revisited,”
*The Journal of Chemical Physics*, vol. 117, no. 23, pp. 10548–10560, 2002. View at Publisher · View at Google Scholar · View at Scopus - J. Cao, Z. Zhang, C. Zhang, W. Bian, and Y. Guo, “Kinetic study on the H+SiH
_{4}abstraction reaction using an*ab initio*potential energy surface,”*The Journal of Chemical Physics*, vol. 134, no. 2, 2011. View at Publisher · View at Google Scholar - H. J. Werner and P. J. Knowles, “A second order multiconfiguration SCF procedure with optimum convergence,”
*The Journal of Chemical Physics*, vol. 82, no. 11, pp. 5053–5063, 1985. View at Scopus - H. J. Werner and W. Meyer, “A quadratically convergent multiconfiguration-self-consistent field method with simultaneous optimization of orbitals and Cl coefficients,”
*The Journal of Chemical Physics*, vol. 73, no. 5, pp. 2342–2356, 1980. View at Scopus - H. J. Werner and W. Meyer, “A quadratically convergent MCSCF method for the simultaneous optimization of several states,”
*The Journal of Chemical Physics*, vol. 74, no. 10, pp. 5794–5801, 1981. View at Scopus - H. J. Werner and P. J. Knowles, “An efficient internally contracted multiconfiguration-reference configuration interaction method,”
*The Journal of Chemical Physics*, vol. 89, no. 9, pp. 5803–5814, 1988. View at Scopus - D. E. Woon and T. H. Dunning, “Gaussian basis sets for use in correlated molecular calculations. V. Core-valence basis sets for boron through neon,”
*The Journal of Chemical Physics*, vol. 103, no. 11, pp. 4572–4585, 1995. View at Scopus - A. K. Wilson, T. Van Mourik, and T. H. Dunning, “Gaussian basis sets for use in correlated molecular calculations. VI. Sextuple zeta correlation consistent basis sets for boron through neon,”
*Journal of Molecular Structure: THEOCHEM*, vol. 388, no. 1–3, pp. 339–349, 1996. View at Scopus - H. Partridge and D. W. Schwenke, “The determination of an accurate isotope dependent potential energy surface for water from extensive
*ab initio*calculations and experimental data,”*The Journal of Chemical Physics*, vol. 106, no. 11, pp. 4618–4639, 1997. View at Scopus - O. L. Polyansky, A. G. Császár, S. V. Shirin et al., “High-accuracy
*ab initio*rotation-vibration transitions for water,”*Science*, vol. 299, no. 5606, pp. 539–542, 2003. View at Publisher · View at Google Scholar · View at Scopus - Z. Zhang, H. Ma, and W. Bian, “Accurate quantum mechanical study of the Renner-Teller effect in the singlet CH
_{2},”*The Journal of Chemical Physics*, vol. 135, Article ID 154303, 10 pages, 2011. - H.-J. Werner, P. J. Knowles, R. Lindh, et al., MOLPRO, version 2006.1, a package of
*ab initio*programs. - W. Bian and H.-J. Werner, “Global
*ab initio*potential energy surfaces for the CIH_{2}reactive system,”*The Journal of Chemical Physics*, vol. 112, no. 1, pp. 220–229, 2000. - J. R. Flores and R. J. Gdanitz, “Accurately solving the electronic Schrödinger equation of small atoms and molecules using explicitly correlated (r
_{12}-)MR-CI. VIII. Valence excited states of methylene (CH_{2}),”*The Journal of Chemical Physics*, vol. 123, no. 14, Article ID 144316, 8 pages, 2005. View at Publisher · View at Google Scholar · View at Scopus - G. Duxbury and C. Jungen, “Effects of orbital angular momentum in CH
_{2}The Renner-Teller effect,”*Journal of Polymer Science B*, vol. 63, no. 6, pp. 981–998, 1988. - D. C. Comeau, I. Shavitt, P. Jensen, and P. R. Bunker, “An
*ab initio*determination of the potential-energy surfaces and rotation-vibration energy levels of methylene in the lowest triplet and singlet states and the singlet—triplet splitting,”*The Journal of Chemical Physics*, vol. 90, no. 11, pp. 6491–6500, 1989. View at Scopus - H. Petek, D. J. Nesbitt, D. C. Darwin, and C. Bradley Moore, “Visible absorption and magnetic
*‐*rotation spectroscopy of^{1}CH_{2}: The analysis of the $\stackrel{\u0303}{\mathrm{b}}$${}^{1}{\mathrm{B}}_{1}$ state,”*The Journal of Chemical Physics*, vol. 86, no. 3, pp. 1172–1188, 1987. View at Scopus - G. V. Hartland, D. Qin, and H. L. Dai, “Fourier transform dispersed fluorescence spectroscopy: observation of new vibrational levels in the 5000–8000 ${\mathrm{c}\mathrm{m}}^{-1}$ region of $\stackrel{\u0303}{\mathrm{a}}$${}^{1}{A}_{1}$ CH
_{2},”*The Journal of Chemical Physics*, vol. 98, no. 3, pp. 2469–2472, 1993. View at Scopus - W. H. Green, I. C. Chen, H. Bitto, D. R. Guyer, and C. B. Moore, “New vibrational bands of CH
_{2}($\stackrel{\u0303}{\mathrm{b}}$${}^{1}{\mathrm{B}}_{1}$),”*Journal of Molecular Spectroscopy*, vol. 138, no. 2, pp. 614–629, 1989. View at Scopus - L. J. Doriol, F. Gatti, C. Iung, and H. D. Meyer, “Computation of vibrational energy levels and eigenstates of fluoroform using the multiconfiguration time-dependent Hartree method,”
*The Journal of Chemical Physics*, vol. 129, no. 22, Article ID 224109, 9 pages, 2008. View at Publisher · View at Google Scholar · View at Scopus - H. D. Meyer, F. L. Quéré, C. Léonard, and F. Gatti, “Calculation and selective population of vibrational levels with the Multiconfiguration Time-Dependent Hartree (MCTDH) algorithm,”
*Chemical Physics*, vol. 329, no. 1-3, pp. 179–192, 2006. View at Publisher · View at Google Scholar · View at Scopus - H.-D. Meyer, U. Manthe, and L. S. Cederbaum, “The multi-configurational time-dependent Hartree approach,”
*Chemical Physics Letters*, vol. 165, no. 1, pp. 73–78, 1990. View at Scopus - M. H. Beck, A. Jäckle, G. A. Worth, and H. D. Meyer, “The multiconfiguration time-dependent Hartree (MCTDH) method: a highly efficient algorithm for propagating wavepackets,”
*Physics Report*, vol. 324, no. 1, pp. 1–105, 2000. View at Scopus - G. A. Worth, M. H. Beck, A. Jäckle, and H.-D. Meyer, The MCTDH Package, Version 8.2, 2000, University of Heidelberg, Germany. H.-D. Meyer, Version 8.3, 2002, Version 8.4, 2007, http://mctdh.uni-hd.de.