Vibrational excitation in the transition state:: The CH4+H→CH3+H2 reaction rate constant in an extended temperature interval

Accurate quantum mechanical results for the thermal rate constant of the prototypical six atom reaction, CH4+H-->CH3+H-2, are reported in this article. Previous k(T) results for temperature values below 500 K are extended up to 1000 K. This is achieved employing a combined iterative diagonalization and statistical sampling approach for the evaluation of the flux correlation function. The accurate reaction rate data obtained for the extended temperature range is used to test several approximations related to the transition state theory. The study especially focuses on the contribution of vibrationally excited states of the activated complex to the thermal rate constant. (C) 2002 American Institute of Physics.