Dynamic isotope effect on the product energy partitioning in CH2OH+-> CHO++H-2

Abstract

The deuterium isotope effect on the product energy partitioning in the title reaction was investigated both experimentally and theoretically. The measured kinetic energy release (KER) showed a significant dependence on the position of deuteration. A reliable potential energy surface of the reaction was constructed from ab initio results using the recently developed interpolation algorithm. The classical trajectory calculation on this surface well reproduced the experimental finding. Close inspection of the potential energy surface revealed that the isotope effect on KER and the product rotations arose from the alteration of the symmetry of the reaction path near the transition state induced by the mass change upon isotopic substitution. The product vibrations were found to be affected by the change in the coupling constants which also arose from the mass-dependent change in the reaction path. Possibility of the quantum mechanical tunneling was also considered. Tunneling-corrected classical trajectory results were in excellent agreement with the experimental ones, indicating that the reaction proceeds via barrier penetration below the threshold. (C) 1998 American Institute of Physics. [S0021-9606(98)03137-7].