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Chau FT, Mok DK, Lee EP, et al. The singlet-triplet separation in CF2: state-of-the-art ab initio calculations and Franck-Condon simulations including anharmonicity. Chemphyschem. 2005;6(10):2037-45doi: 10.1002/cphc.200500114.
Chau, F. T., Mok, D. K., Lee, E. P., & Dyke, J. M. (2005). The singlet-triplet separation in CF2: state-of-the-art ab initio calculations and Franck-Condon simulations including anharmonicity. Chemphyschem : a European journal of chemical physics and physical chemistry, 6(10), 2037-45. https://doi.org/10.1002/cphc.200500114
Chau, Foo-tim, et al. "The singlet-triplet separation in CF2: state-of-the-art ab initio calculations and Franck-Condon simulations including anharmonicity." Chemphyschem : a European journal of chemical physics and physical chemistry vol. 6,10 (2005): 2037-45. doi: https://doi.org/10.1002/cphc.200500114
Chau FT, Mok DK, Lee EP, Dyke JM. The singlet-triplet separation in CF2: state-of-the-art ab initio calculations and Franck-Condon simulations including anharmonicity. Chemphyschem. 2005 Oct 14;6(10):2037-45. doi: 10.1002/cphc.200500114. PMID: 16208745.
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Chemphyschem. 2005 Oct 14;6(10):2037-45. doi: 10.1002/cphc.200500114.

The singlet-triplet separation in CF2: state-of-the-art ab initio calculations and Franck-Condon simulations including anharmonicity.

Chemphyschem : a European journal of chemical physics and physical chemistry

Foo-tim Chau, Daniel K W Mok, Edmond P F Lee, John M Dyke

Affiliations

  1. Department of Applied Biology and Chemical Technology, Hong Kong Polytechnic University, Hung Hom, Hong Kong. [email protected]

PMID: 16208745 DOI: 10.1002/cphc.200500114

Abstract

Geometrical parameters, vibrational frequencies and relative electronic energies of the X2B1 state of CF2- and the X1A1 and ã3B1 states of CF2 have been calculated. Core-electron effects on the computed minimum-energy geometries and relative electronic energies have been investigated, and relativistic contributions to the computed relative electronic energies calculated. Potential energy functions of the X2B1 state of CF2- and the X1A1 and ã3B1 states of CF2 have been determined, and anharmonic vibrational wavefunctions of these states calculated variationally. Franck-Condon factors including anharmonicity and Duschinsky rotation have been computed and used to simulate the ã-X emission spectrum of CF2 determined by S. Koda [Chem. Phys. Lett. 1978, 55, 353] and the 364 nm laser photodetachment spectrum of CF2- obtained by R. L. Schwartz et al. [J. Phys. Chem. A 1999, 103, 8213]. Comparison between theory and experiment shows that the theoretical approach benchmarked in the present study is able to give highly reliable positions for the CF2(X1A1) + e <-- CF2-(X2B1) and CF2(ã3B1) + e <-- CF2-(X2B1) bands in the photoelectron spectrum of CF2- and a reliable singlet-triplet gap for CF2. It is therefore concluded that the same theoretical approach should give reliable simulated CCl2(X1A1) + e <-- CCl2-(X2B1) and CCl2(ã3B1) + e <-- CCl2-(X2B1) bands in the photodetachment spectrum of CCl2- and a reliable singlet-triplet gap for CCl2.

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