Accurate quantum calculations of the reaction rates for H/D+ CH4

作者：van Harrevelt Rob^*; Nyman Gunnar; Manthe Uwe

来源：Journal of Chemical Physics, 2007, 126(8): 084303.

DOI：10.1063/1.2464102

In previous work [T. Wu, H. J. Werner, and U. Manthe, Science 306, 2227 (2004)], accurate quantum reaction rate calculations of the rate constant for the H+CH4 -> CH3+H-2 reaction have been presented. Both the electronic structure calculations and the nuclear dynamics calculations are converged with respect to the basis sets employed. In this paper, the authors apply the same methodology to an isotopic variant of this reaction: D+CH4 -> CH3+HD. Accurate rate constants are presented for temperatures between 250 and 400 K. For temperatures between 400 and 800 K, they use a harmonic extrapolation to obtain approximate rate constants for H/D+CH4. The calculations suggest that the experimentally reported rate constants for D+CH4 are about a factor of 10-20 too high. For H+CH4, more accurate experiments are available and agreement is much better: the difference is less than a factor of 2.6. The kinetic isotope effect for the H/D+CH4 reactions is studied and compared with experiment and transition state theory (TST) calculations. Harmonic TST was found to provide a good description of the kinetic isotope effect.

• 出版日期2007-2-28