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

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].
Publisher
AMER INST PHYSICS
Issue Date
1998-10
Language
English
Keywords

CLASSICAL TRAJECTORY SIMULATION; CHEMICAL-REACTIONS; RELEASE DISTRIBUTION; REACTION COORDINATE; PATH; MOLECULES; ELIMINATION; SURFACES; INTERPOLATION; DISSOCIATION

Citation

JOURNAL OF CHEMICAL PHYSICS, v.109, no.13, pp.5363 - 5371

ISSN
0021-9606
DOI
10.1063/1.477155
URI
http://hdl.handle.net/10203/225428
Appears in Collection
CH-Journal Papers(저널논문)
Files in This Item
There are no files associated with this item.
  • Hit : 19
  • Download : 0
  • Cited 0 times in thomson ci
This item is cited by other documents in WoS
⊙ Detail Information in WoSⓡClick to seewebofscience_button
⊙ Cited 11 items in WoSClick to see citing articles inrecords_button

qr_code

  • mendeley

    citeulike


rss_1.0 rss_2.0 atom_1.0