Photochemistry in a dense manifold of electronic states: Photodissociation of CH{sub 2}ClBr

Journal Article · Fri Sep 14 04:00:00 EDT 2012 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4747704· OSTI ID:22099020

Valero, Rosendo ^[1]; Truhlar, Donald G. ^[2]

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1. Department of Chemistry, University of Coimbra, Coimbra (Portugal)
2. 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: 22099020
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 10 Vol. 137; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
APPROXIMATIONS
DISSOCIATION
L-S COUPLING
ORGANIC BROMINE COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
PERTURBATION THEORY
PHOTOCHEMISTRY
PHOTOLYSIS
POTENTIAL ENERGY
SPIN
SURFACES