Reactions over multiple, interconnected potential wells: unimolecular and bimolecular reactions on a C3H5 potential.
In this article we analyze quantitatively and discuss in detail a number of reactions that take place on a C3H5 potential. These reactions include the reaction of hydrogen atoms with allene and propyne, the reaction of methyl with acetylene, the isomerization of cyclopropyl to allyl, and the dissociation of allyl, 1-propenyl, and 2-propenyl. The theory employs high-level electronic-structure methods to characterize the potential energy surface, RRKM theory to calculate microcanonical, J-resolved rate coefficients, and master-equation methods to determine phenomenological rate coefficients, k(T,p). The agreement between our theory and the experimental results available is very good. The final theoretical results are cast in a form that is convenient for use in chemical kinetics modeling.
Miller
James A
JA
Combustion Research Facility, Sandia National Laboratories, Livermore, California 94551-0969, USA. jamille@sandia.gov
Senosiain
Juan P
JP
Klippenstein
Stephen J
SJ
Georgievskii
Yuri
Y