When Rate Constants Are Not Enough
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- 作者：John R. Barker ; Michael Frenklach ; David M. Golden
- 刊名：Journal of Physical Chemistry A
- 出版年：2015
- 出版时间：July 16, 2015
- 年：2015
- 卷：119
- 期：28
- 页码：7451-7461
- 全文大小：582K
- ISSN：1520-5215
文摘
Real-world chemical systems consisting of multiple isomers and multiple reaction channels often react significantly prior to attaining a steady state energy distribution (SED). Detailed elementary reaction models, which implicitly require SED conditions, may be invalid when non-steady-state energy distributions (NSED) exist. NSED conditions may result in reaction rates and product yields that are different from those expected for SED conditions, although this problem is to some extent reduced by using phenomenological models and rate constants. The present study defines pragmatic diagnostics useful for identifying NSED conditions in stochastic master equation simulations. A representative example is presented for each of four classes of common combustion species: RO2 radicals, aliphatic hydrocarbons, alkyl radicals, and polyaromatic radicals. An example selected from the seminal work of Tsang et al. demonstrates that stochastic simulations and eigenvalue methods for solving the master equation predict the same NSED effects. NSED effects are common under relatively moderate combustion conditions, and accurate simulations may require a master equation analysis.