Predictive a priori pressure-dependent kinetics

The ability to predict the pressure dependence of chemical reaction rates would be a great boon to kinetic modeling of processes such as combustion and atmospheric chemistry. This pressure dependence is intimately related to the rate of collision-induced transitions in energy E and angular momentum...

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Bibliographic Details
Published in:Science (American Association for the Advancement of Science) 2014-12, Vol.346 (6214), p.1212-1215
Main Authors: Jasper, Ahren W., Pelzer, Kenley M., Miller, James A., Kamarchik, Eugene, Harding, Lawrence B., Klippenstein, Stephen J.
Format: Article
Language:English
Subjects:
A priori knowledge
Angular momentum
Atmospheric chemistry
Chemical reactions
Chemistry
Combustion
Energy transfer
Experimental data
Experimental results
Kinetics
Materials
Organic Chemistry
Pressure dependence
Temperature dependence
Transfer Rates (College)
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Summary:The ability to predict the pressure dependence of chemical reaction rates would be a great boon to kinetic modeling of processes such as combustion and atmospheric chemistry. This pressure dependence is intimately related to the rate of collision-induced transitions in energy E and angular momentum J. We present a scheme for predicting this pressure dependence based on coupling trajectory-based determinations of moments of the E,J-resolved collisional transfer rates with the two-dimensional master equation. This completely a priori procedure provides a means for proceeding beyond the empiricism of prior work. The requisite microcanonical dissociation rates are obtained from ab initio transition state theory. Predictions for the CH4 = CH3 + H and C2H3 = C2H2 + H reaction systems are in excellent agreement with experiment.
ISSN:0036-8075
1095-9203
DOI:10.1126/science.1260856