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A centrifugal-sudden distorted-wave study of isotope effects for the reactions Cl+HCl r arrow ClH+Cl and Cl+DCl r arrow ClD+Cl

Journal Article · · Journal of Chemical Physics; (USA)
DOI:https://doi.org/10.1063/1.459624· OSTI ID:6149872
 [1]; ;  [2]
  1. Theoretical Chemistry Group, Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439 (USA)
  2. Department of Chemistry, University of Manchester, Manchester M13 9PL (Great Britain)

A quantum calculation has been performed using the centrifugal-sudden distorted-wave (CSDW) method for the three-dimensional Cl+DCl{r arrow}ClD+Cl reaction. Three potential energy surfaces have been employed: two extended London--Eyring--Polanyi--Sato surfaces (denoted Bondi--Connor--Manz--Roemelt (BCMR) and Persky--Kornweitz 3 (PK3)) and a scaled and fitted {ital ab} {ital initio} one (denoted sf-POLCI). Quantities calculated include: cumulative reaction probabilities, integral cross sections, rotational product distributions, and rate coefficients. Differential cross reactions are also reported for the PK3 surface, which are compared with the results from a simple semiclassical optical model (close agreement is found). We also compare the Cl+DCl results with earlier CSDW calculations for Cl+HCl{r arrow}ClH+Cl. The rotational distributions are strongly perturbed by isotope substitution and are sensitive to variations in the potential surface. In contrast, the H and D rate coefficients for all three surfaces agree with experimental values, except for Cl+DCl on PK3.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL
DOE Contract Number:
W-31109-ENG-38
OSTI ID:
6149872
Journal Information:
Journal of Chemical Physics; (USA), Journal Name: Journal of Chemical Physics; (USA) Vol. 93:8; ISSN JCPSA; ISSN 0021-9606
Country of Publication:
United States
Language:
English