Photochemistry in a dense manifold of electronic states: Photodissociation of CH2ClBr

Rosendo Valero, Donald G. Truhlar

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We report electronically nonadiabatic dynamics calculations including spin-orbit coupling for the photodissociation of CH2ClBr to yield Cl(2P3/2), Cl(2P1/2), Br( 2P3/2), and Br(2P1/2). The potential energy is a 24 × 24 matrix (divided up here into four 6 × 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.

Original languageEnglish (US)
Article number22A539
JournalJournal of Chemical Physics
Issue number22
StatePublished - Dec 14 2012


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