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

1981; American Institute of Physics; Volume: 75; Issue: 5 Linguagem: Inglês

10.1063/1.442286

1520-9032

William H. Miller, Shenghua Shi,

Photochemistry and Electron Transfer Studies

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.