Recent developments and applications of the ab initio transition state theory based master equation approach for obtaining a priori theoretical kinetics predictions will be summarized. We will begin by reviewing the chemically significant eigenmode (CSE) approach to extracting phenomenological rate coefficients for use in combustion mechanisms. Illustrative applications to some key problems in combustion chemistry will be used to highlight how the CSE approach resolves a number of the difficulties that arise with other more traditional species time profile based approaches. We will also describe a novel direct implementation of trajectory calculated energy transfer parameters within the 2-dimensional master equation in energy and total angular momentum. A study of propyl radical oxidation will illustrate the effect of a second addition occurring on the same timescale as the vibrational relaxation process.

Ab initio transition state theory based master equation approach: Advances and applications to kinetic predictions for combustion chemistry

245th National Meeting (2013)

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