The Journal of Physical Chemistry A· 2013Q2
Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions
- 717citations
- Q2SCImago
- 2013year
Short summary
A new formulation of the master equation simplifies the analysis of complex chemical reactions by focusing only on isomer populations, yielding compact rate coefficients for all reaction types.
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Key points
- Reformulated master equation focuses on microscopic isomer populations.
- Reactants and products are treated as sources and sinks.
- Yields compact rate coefficients for isomerization, bimolecular, and mixed reactions.
- Detailed balance condition is confirmed.
- Method is adaptable for cases where chemical eigenvalues approach energy relaxation timescales.
AI-generated from the title and abstract; the full text is not read.
Abstract
We consider an alternative formulation of the master equation for complex-forming chemical reactions with multiple wells and bimolecular products. Within this formulation the dynamical phase space consists of only the microscopic populations of the various isomers making up the reactive complex, while the bimolecular reactants and products are treated equally as sources and sinks. This reformulation yields compact expressions for the phenomenological rate coefficients describing all chemical processes, i.e., internal isomerization reactions, bimolecular-to-bimolecular reactions, isomer-to-bimolecular reactions, and bimolecular-to-isomer reactions. The applicability of the detailed balance condition is discussed and confirmed. We also consider the situation where some of the chemical eigenvalues approach the energy relaxation time scale and show how to modify the phenomenological rate coefficients so that they retain their validity.
The authors' abstract, as published at the source. The Journal of Physical Chemistry A, 2013 · DOI ↗
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Field: Physical and Theoretical Chemistry
Physical and Theoretical ChemistryChemistry