Density functional theory applied to hydrogen abstraction reactions
- Exxon Research and Engineering Co., Annandale, NJ (United States)
Hydrogen atone abstraction reactions dominate the free-radical chemistry of many hydrocarbons. Accurate estimates of their rate constants are critical for modeling combustion, atmospheric chemistry and other important processes. Many hydrogen abstraction reactions show curved Arrhenius plots, making extrapolations from experimental temperatures to relevant reaction temperatures difficult. For low temperature saturated hydrocarbon reactions good experimental data are available, but for higher temperatures, rate constant data are needed. Extrapolation of abstraction rate constants from experimental data on reactions involving olefins is further complicated by parallel, competing radical addition paths. A quantitative approach is taken through new theoretical techniques such as Density Functional Theory, which allows accurate calculations on moderately large open shell transition states. Density Functional Theory calculations as input to Transition State Theory provide a theoretical approach for predicting rate constants for hydrogen atom abstraction reactions. Results are compared with experimental data where available.
- OSTI ID:
- 126871
- Report Number(s):
- CONF-950402--
- Country of Publication:
- United States
- Language:
- English
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