title: Predictive a priori pressure-dependent kinetics.
abstract: 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.
authors.affiliation: Combustion Research Facility, Sandia National Laboratories, MS 9055, Livermore, CA 94551-0969, USA.
authors.forename: Ahren W
authors.initials: AW
authors.lastname: Jasper
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA.
authors.forename: Kenley M
authors.initials: KM
authors.lastname: Pelzer
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA.
authors.forename: James A
authors.initials: JA
authors.lastname: Miller
authors.affiliation: Combustion Research Facility, Sandia National Laboratories, MS 9055, Livermore, CA 94551-0969, USA.
authors.forename: Eugene
authors.initials: E
authors.lastname: Kamarchik
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA.
authors.forename: Lawrence B
authors.initials: LB
authors.lastname: Harding
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, IL 60439, USA. sjk@anl.gov.
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Klippenstein