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Semiclassical Transition State Theory - A New Perspective

Rigoberto Hernandez and William H. Miller

Department of Chemistry, University of California, and
Chemical Sciences Division, Lawrence Berkeley Laboratory
Berkeley, California 94720


The semiclassical transition state theory (SCTST) introduced by Miller, Hernandez, Handy, Jayatilaka and Willetts[1] requires the inversion of an (effectively integrable) Hamiltonian with respect to the action of the reactive coordinate. In this paper, it is shown that the inversion may be avoided in computing the thermal rate constant; the resulting expression also provides an appealing link to conventional transition state theory. This reformulation of the SCTST rate is illustrated by application to the bimolecular reaction, tex2html_wrap_inline343 , and to the unimolecular dissociation, tex2html_wrap_inline345 .