Evaluation of resonance contributions to thermal reaction rates using quantum flux correlation functions

Mark Thachuk, George C Schatz

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Abstract

We consider the evaluation of thermal rate constants using quantum flux correlation functions for chemical reactions in which metastable states (resonances) play a significant role in the reaction dynamics. The evaluation of rate constants is hindered in this case because of slowly decaying oscillations in the correlation functions but we show that it is possible to remove these oscillations by projecting the resonant states from the wave packets used to calculate flux correlation functions. These projected states do contribute to the reactive flux, but it is not difficult to include for this using the resonance widths. The resulting theory thus uses a combination of short time wave packet propagation for the direct contribution, and bound-state methods for the resonant contribution, thereby achieving a balance between the strengths of time dependent and time independent methods. We illustrate this theory through an application to a simple one-dimensional potential.

Original languageEnglish
Pages (from-to)6577-6585
Number of pages9
JournalJournal of Chemical Physics
Volume101
Issue number8
Publication statusPublished - 1994

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ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

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