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Unified semiclassical perturbation and infinite order sudden approximation, with application to the reaction path Hamiltonian model

Journal Article · · J. Chem. Phys.; (United States)
DOI:https://doi.org/10.1063/1.442286· OSTI ID:6183244

It is shown how two popular approximate dynamical models: the semiclassical perturbation (SCP) approximation and the infinite order sudden (IOS) approximation: can be combined in a consistent way that includes the correct features of both. Application of this unified SCP--IOS approximation to the reaction path Hamiltonian model of Miller, Handy, and Adam (J. Chem. Phys. 72, 99 (1980)) leads to extremely simple, explicit formulas for the reactive S matrix, product state distrubutions, etc., which can be readily applied to polyatomic systems. Initial numerical tests on a simple model problem indicate that the model is of useful accuracy.

Research Organization:
Department of Chemistry and Materials and Molecular Research Division of the Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
OSTI ID:
6183244
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 75:5; ISSN JCPSA
Country of Publication:
United States
Language:
English