title: Comparison of quantum dynamics and quantum transition state theory estimates of the H + CH4 reaction rate.
abstract: Thermal rate constants are calculated for the H + CH(4) --> CH(3) + H(2) reaction employing the potential energy surface of Espinosa-Garcia (Espinosa-Garcia, J. J. Chem. Phys. 2002, 116, 10664). Two theoretical approaches are used. First, we employ the multiconfigurational time-dependent Hartree method combined with flux correlation functions. In this way rate constants in the range 225-400 K are obtained and compared with previous results using the same theoretical method but the potential energy surface of Wu et al. (Wu, T.; Werner, H.-J.; Manthe, U. Science 2004, 306, 2227). It is found that the Espinosa-Garcia surface results in larger rate constants. Second, a harmonic quantum transition state theory (HQTST) implementation of instanton theory is used to obtain rate constants in a temperature interval from 20 K up to the crossover temperature at 296 K. The HQTST estimates are larger than MCTDH ones by a factor of about three in the common temperature range. Comparison is also made with various tunneling corrections to transition state theory and quantum instanton theory.
authors.affiliation: Department of Chemistry, Physical Chemistry, University of Gothenburg, SE-41296 Gothenburg, Sweden.
authors.forename: Stefan
authors.initials: S
authors.lastname: Andersson
authors.forename: Gunnar
authors.initials: G
authors.lastname: Nyman
authors.forename: Andri
authors.initials: A
authors.lastname: Arnaldsson
authors.forename: Uwe
authors.initials: U
authors.lastname: Manthe
authors.forename: Hannes
authors.initials: H
authors.lastname: Jónsson