Time-dependent wave packet state-to-state dynamics of H/D + HCl/DCl reactions
Date of Issue2013
School of Physical and Mathematical Sciences
The H/D + HCl/DCl (v0 = 0, j0 = 0) reactions were investigated in the gas phase using the reactant coordinate based time-dependent wave packet method on the BW2 PES [W. Bian and H.-J. Werner, J. Chem. Phys. 112, 220 (2000)]. The total and state-to-state integral and differential cross sections of both the abstraction and the exchange channels were reported over the energy range from threshold to 2.0 eV. The theoretical total exchange integral cross sections agree well with Volpp's experimental measurements but differ from Polanyi's experimental results for H + DCl reaction. The theoretical total abstraction integral cross sections are more than twice as large as the experimental results from the two groups for the H + HCl/DCl reactions. For the four isotope combinations, the total exchange integral cross sections increase monotonically with collisional energy while the abstraction integral cross sections start to decrease at relatively high collision energies. And the abstraction products are predominantly backward and sideways scattered while the exchange products are almost backward scattered. For the two channels, the D + HCl reaction presents the highest reactivity, the H + DCl reaction presents the lowest reactivity, and the H + HCl and D + DCl reactions are in between with the H + HCl reaction having a slightly larger reactivity.
The journal of chemical physics
© 2013 American Institute of Physics. This paper was published in The Journal of Chemical Physics and is made available as an electronic reprint (preprint) with permission of American Institute of Physics. The paper can be found at the following official DOI: [http://dx.doi.org/10.1063/1.4790116]. 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.