Sum over Histories Representation for Chemical Kinetics.
A new representation for chemical kinetics is introduced that is based on a sum over histories formulation that employs chemical pathways defined at a molecular level. The time evolution of a chemically reactive system is described by enumerating the most important pathways followed by a chemical moiety. An explicit formula for the pathway probabilities is derived and takes the form of an integral over a time-ordered product. When evaluating long pathways, the time-ordered product has a simple Monte Carlo representation that is computationally efficient. A small numerical stochastic simulation was used to identify the most important paths to include in the representation. The method was applied to a realistic H2/O2 combustion problem and is shown to yield accurate results.
†Department of Chemistry and Biochemistry, University of Colorado, Box 215, Boulder, Colorado 80309, United States.
Shirong
S
Bai
†Department of Chemistry and Biochemistry, University of Colorado, Box 215, Boulder, Colorado 80309, United States.
Dingyu
D
Zhou
‡Chemical Science and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
Michael J
MJ
Davis
†Department of Chemistry and Biochemistry, University of Colorado, Box 215, Boulder, Colorado 80309, United States.
Rex T
RT
Skodje
Feynman; Monte Carlo; combustion; kinetics; pathway; rate theory; time-ordered product