Determining phenomenological rate coefficients from a time-dependent, multiple-well master equation: “species reduction” at high temperatures
Literature Information
James A. Miller, Stephen J. Klippenstein
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 (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.













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