Determining phenomenological rate coefficients from a time-dependent, multiple-well master equation: “species reduction” at high temperatures

Literature Information

Publication Date 2013-02-13
DOI 10.1039/C3CP44337J
Impact Factor 3.676
Authors

James A. Miller, Stephen J. Klippenstein


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Abstract

In this article we discuss at length the determination of phenomenological rate coefficients from the solution to a time-dependent, multiple-well master equation. Both conservative and non-conservative formulations are considered. The emphasis is placed on how to handle the situation when a CSE (chemically significant eigenvalue of the transition matrix) merges with the quasi-continuum of IEREs (internal energy relaxation eigenvalues), indicating that one or more chemical reactions begin to take place on vibrational–rotational relaxation time scales. The methodology is illustrated with four examples.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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