Comparison of Quantum Dynamics and Quantum Transition State Theory Estimates of the H+CH4 Reaction Rate

Andersson S, Nyman G, Arnaldsson A, Manthe U, Jonsson H. Comparison of Quantum Dynamics and Quantum Transition State Theory Estimates of the H+CH4 Reaction Rate. Journal of Physical Chemistry A. 2009;113(16):4468-4478.Thermal rate constants are calculated for the H + CH4 -> CH3 + 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