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 language | English (US) |
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Pages (from-to) | 4882-4888 |
Number of pages | 7 |
Journal | The Journal of chemical physics |
Volume | 79 |
Issue number | 10 |
DOIs | |
State | Published - 1983 |