Small-curvature adiabatic approximation for reaction-path reduced-dimensionality effective Hamiltonian

Rex T. Skodje, Donald G Truhlar

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

Beginning with the Miller-Handy-Adams reaction-path Hamiltonian, which is applicable to chemical reactions and photodissociation processes, we classify the modes as one reaction coordinate, (f-1) strongly coupled modes, and (F-f) weakly coupled modes. We derive a reduced-dimensionality Hermitian Hamiltonian for f explicit modes such that the (F-f) weakly coupled modes are treated adiabatically and their coupling to the reaction coordinate due to reaction-path curvature is included implicitly. The reduction is achieved two ways: one based on a small-curvature-tunneling approximation and one based on a more general semiclassical-path assumption for the weakly coupled modes.

Original languageEnglish (US)
Pages (from-to)4882-4888
Number of pages7
JournalThe Journal of chemical physics
Volume79
Issue number10
DOIs
StatePublished - 1983

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