Full-Dimensional Quantum Dynamical Studies of the Cl + HOD → HCl/DCl + OD/OH Reaction: Bond Selectivity and Isotopic Branching Ratio
Date of Issue2015
School of Physical and Mathematical Sciences
Full-dimensional quantum dynamical calculations are carried out to study the mode specificity, bond selectivity, and isotopic branching ratio of the Cl + HOD reaction on an accurate global potential energy surface. Total reaction cross sections have been computed for several low-lying vibrational states of HOD. Our results confirm the experimental observed vibrationally promoted bond cleavage, in which the breaking of the OH(OD) bond is strongly enhanced by the OH(OD) excitation. These results are rationalized by the recently proposed sudden vector projection model. In addition, the OH/OD branching ratio as a function of energy is investigated and rationalized by a reorientation effect.
The Journal of Physical Chemistry A
© 2015 American Chemical Society. This paper was published inThe Journal of Physical Chemistry A and is made available as an electronic reprint (preprint) with permission of American Chemical Society. The published version is available at: [http://dx.doi.org/10.1021/acs.jpca.5b06230]. One print or electronic copy may be made for personal use only. Systematic or multiple reproduction, distribution to multiple locations via electronic or other means, duplication of any material in this paper for a fee or for commercial purposes, or modification of the content of the paper is prohibited and is subject to penalties under law.