Direct ab initio dynamics study on the rate constants and kinetics isotope effects of CH3O+H→CH2O+H2 reaction
Authors: Li Qian Shu , Zhang Yue , Zhang Shaowen 
Published: November 2004

We present a direct ab initio dynamics study of thermal rate constants of the hydrogen abstraction reaction of CH3O+H→CH2O+H2. The unrestricted Becke’s half-and-half hybrid functional using the Lee–Yang–Parr correlation functional with Dunning’s correlation consistent polarized valence double-ζ basis set, the unrestricted quadratic configuration interaction calculation including single and double substitutions with Dunning’s correlation consistent polarized valence double-ζ basis set, and the unrestricted quadratic configuration interaction calculation including single and double substitutions with a triples contribution with Dunning’s correlation consistent polarized valence triple-ζ basis set methods were employed to optimize the structures and to calculate frequencies for all stationary points. Minimum energy paths were obtained by the unrestricted Becke’s half-and-half hybrid functional using the Lee–Yang–Parr correlation functional and the unrestricted quadratic configuration interaction calculation including single and double substitutions with the same Dunning’s correlation consistent polarized valence double-ζ basis set levels of theory. No barrier is found at the unrestricted Becke’s half-and-half hybrid functional using the Lee–Yang–Parr correlation functional with Dunning’s correlation consistent polarized valence double-ζ basis set level of theory in contrast to a small barrier of 1.43 kcal mol−1 at the unrestricted quadratic configuration interaction calculation including single and double substitutions with Dunning’s correlation consistent polarized valence double-ζ basis set level of theory. In particular, the barrier vanishes as the energies along the minimum energy path MEP are refined at the unrestricted quadratic configuration interaction calculation including single and double substitutions with a triples contribution with Dunning’s correlation consistent polarized valence triple-ζ basis set level of theory. Smaller barriers of 0.47 and 0.17 kcal mol−1 were obtained at the unrestricted quadratic configuration interaction calculation including single and double substitutions with a triples contribution with Dunning’s correlation consistent polarized valence triple-ζ basis set and the unrestricted quadratic configuration interaction calculation including single and double substitutions with a triples contribution with Dunning’s correlation consistent polarized valence triple-ζ basis set based on the geometries at the unrestricted quadratic configuration interaction calculation including single and double substitutions with Dunning’s correlation consistent polarized valence triple-ζ basis set levels of theory, respectively. The forward rate constants are evaluated with the canonical variational transition state theory in the temperature range of 300–2500 K. The calculated forward rate constants at the unrestricted quadratic configuration interaction calculation including single and double substitutions with a triples contribution with Dunning’s correlation consistent polarized valence triple-ζ basis set based on the geometries at the unrestricted quadratic configuration interaction calculation including single and double substitutions with Dunning’s correlation consistent polarized valence double-ζ basis set level of theory are in good agreement with the available experimental data. The kinetic isotope effects are estimated.