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Determining phenomenological rate coefficients from a time-dependent, multiple-well master equation: "species
James A Miller1, Stephen J Klippenstein
1Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Il 60439, USA. jamiller@anl.gov
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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