Photochemistry in a dense manifold of electronic states: Photodissociation of CH{sub 2}ClBr
- Department of Chemistry, University of Coimbra, Coimbra (Portugal)
- Department of Chemistry and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431 (United States)
We report electronically nonadiabatic dynamics calculations including spin-orbit coupling for the photodissociation of CH{sub 2}ClBr to yield Cl({sup 2}P{sub 3/2}), Cl({sup 2}P{sub 1/2}), Br({sup 2}P{sub 3/2}), and Br({sup 2}P{sub 1/2}). The potential energy is a 24 Multiplication-Sign 24 matrix (divided up here into four 6 Multiplication-Sign 6 blocks in a first approximation to the problem), in a spin-coupled fully diabatic representation obtained by combining the spin-free fourfold way with single-center spin-orbit coupling constants. The spin-free calculations are carried out by multiconfiguration quasidegenerate perturbation theory, and the fully diabatic potentials including spin-orbit coupling are fit to a matrix reactive force field. The dynamics are carried out by the coherent switches with decay of mixing method in the diabatic representation. The results show qualitative agreement with experiment.
- OSTI ID:
- 22099134
- Journal Information:
- Journal of Chemical Physics, Vol. 137, Issue 22; Other Information: (c) 2012 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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