A centrifugal sudden distorted wave study of the Cl + HCl → ClH + Cl reaction

Results for a scaled and fitted ab initio potential energy surface having a noncollinear reaction path

George C Schatz, B. Amaee, J. N L Connor

Research output: Contribution to journalArticle

35 Citations (Scopus)

Abstract

We 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° (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°. We also compare our 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 it 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.

Original languageEnglish
Pages (from-to)3190-3195
Number of pages6
JournalJournal of Physical Chemistry
Volume92
Issue number11
Publication statusPublished - 1988

Fingerprint

Potential energy surfaces
potential energy
saddle points
cross sections
coefficients
products
rotational states
Activation energy
Scattering
activation energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

@article{2c87ad034d804ed1b53b1c45533df643,
title = "A centrifugal sudden distorted wave study of the Cl + HCl → ClH + Cl reaction: Results for a scaled and fitted ab initio potential energy surface having a noncollinear reaction path",
abstract = "We 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° (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°. We also compare our 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 it 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.",
author = "Schatz, {George C} and B. Amaee and Connor, {J. N L}",
year = "1988",
language = "English",
volume = "92",
pages = "3190--3195",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "11",

}

TY - JOUR

T1 - A centrifugal sudden distorted wave study of the Cl + HCl → ClH + Cl reaction

T2 - Results for a scaled and fitted ab initio potential energy surface having a noncollinear reaction path

AU - Schatz, George C

AU - Amaee, B.

AU - Connor, J. N L

PY - 1988

Y1 - 1988

N2 - We 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° (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°. We also compare our 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 it 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.

AB - We 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° (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°. We also compare our 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 it 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.

UR - http://www.scopus.com/inward/record.url?scp=0000850995&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000850995&partnerID=8YFLogxK

M3 - Article

VL - 92

SP - 3190

EP - 3195

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 11

ER -