Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 119, Issue 28, Pages 7451-7461Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.5b00640
Keywords
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Funding
- National Science Foundation (Atmospheric and Geospace Sciences)
- NASA (Upper Atmospheric Research Program)
- U.S. Army Corps of Engineers, Humphreys Engineering Center Support Activity [W912HQ-11-C-0035]
- Department of Mechanical Engineering, Stanford University
- Directorate For Geosciences
- Div Atmospheric & Geospace Sciences [1231842] Funding Source: National Science Foundation
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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.
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