Ab initio study on the kinetics of hydrogen abstraction for the H+alkene-->H2+alkenyl reaction class.
Kinetics of the hydrogen abstraction reaction class of the H+alkene has been studied using the reaction class transition state theory (RC-TST) combined with the linear energy relationship (LER) and the barrier height grouping (BHG) approach. The rate constants for the reference reaction, H+C2H4, were obtained by the canonical variational transition state theory (CVT) with the small curvature tunneling (SCT) correction in the temperature range of 300-3000 K. Combined with these data, both the RC-TST/LER, where only reaction energy is needed, and RC-TST/BHG, where no other information is needed, are found to be promising methods for predicting rate constants for a large number of reactions in this reaction class. Our analysis indicates that less than 50% systematic errors on the average exist in the predicted rate constants using the RC-TST/LER or RC-TST/BHG method while in comparison to explicit rate calculations the differences are less than 100% or a factor of 2 on the average.
Huynh
Lam K
LK
Department of Chemistry, University of Utah, 315 S. 1400 E. Rm. 2020, Salt Lake City, Utah 84112, USA.
Panasewicz
Sylwester
S
Ratkiewicz
Artur
A
Truong
Thanh N
TN