Centrifugal sudden distorted wave study of the Cl + HCl. -->. ClH + Cl reaction: results for a scaled fitted ab initio potential energy surface having a noncollinear reaction path
The authors present the results of a centrifugal sudden distorted wave (CSDW) quantum scattering study of the reaction Cl + HCl ..-->.. ClH + Cl. The potential energy surface used in this calculation (denoted sf-POLCI) has been chosen to fit a scaled ab initio surface for Cl-H-Cl angles greater than 150/sup 0/ (angles for which the latter surface has been determined), and to fit an extended London-Eyring-Polanyi-Sato (LEPS) surface at smaller angles. This sf-POLCI surface has a noncollinear Cl-H-Cl saddle point with a Cl-H-Cl angle of 161.4/sup 0/. They also compare their CSDW results with those from a LEPS surface, which has a collinear geometry saddle point, but is otherwise similar to the sf-POLCI surface. Results presented include partial wave reaction probabilities, integral and differential cross sections, product rotational distributions, and thermal rate coefficients. The sf-POLCI results are generally similar to the LEPS results, although there are a few important differences. In particular, the integral cross sections in the threshold region increase more slowly with energy for the sf-POLCI surface. As a result, the activation energy is smaller for the LEPS surface, even though is has the higher barrier. Both the sf-POLCI and LEPS cross sections exhibit high product rotational excitation, with the sf-POLCI products more excited than the LEPS. Also, the rotational state which contributes most to the thermal rate coefficient is higher for the sf-POLCI surface than for the LEPS. For both surfaces the CSDW rate coefficients agree with experiment within the experimental uncertainties.
- Research Organization:
- Argonne National Lab., IL (USA)
- DOE Contract Number:
- W-31109-ENG-38
- OSTI ID:
- 6333296
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:11; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
AMPLITUDES
CHEMICAL REACTIONS
CHLORINE
DISTORTED WAVE THEORY
EIGENVALUES
ELEMENTS
ENERGY
ENERGY LEVELS
EXCITED STATES
GROUND STATES
HALOGENS
HYDROCHLORIC ACID
HYDROGEN COMPOUNDS
INORGANIC ACIDS
MATHEMATICAL MODELS
NONMETALS
POTENTIAL ENERGY
SCATTERING AMPLITUDES