Reduced-dimensionality quantum calculations of the thermal rate coefficient for the Cl+HCl→ClH+Cl reaction: Comparison with centrifugal-sudden distorted wave, coupled channel hyperspherical, and experimental results

Qiyan Sun, Joel M. Bowman, George C Schatz, J. R. Sharp, J. N L Connor

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Abstract

Reduced dimensionality (RD) cumulative reaction probabilities (CRPs) are reported for the Cl + HCl→ClH + Cl reaction using two semiempirical extended London-Eyring-Polanyi-Sato potential energy surfaces. Comparison is made with CRPs from centrifugal-sudden distorted wave (CSDW) calculations, and with accurate coupled channel hyperspherical (CCH) CRPs for total angular momentum quantum number J=0. Rotational and bending energy-shift approximations are applied to the CCH CRPs for J=0 to obtain approximate CRPs for J>0. A test of this approximation is made using CSDW partial wave CRPs. New expressions for the thermal rate coefficient are derived using these approximations. The rate coefficients calculated from RD and energy-shifted CCH CRPs are in excellent agreement with each other. They also agree well with the CSDW and experimental rate coefficients.

Original languageEnglish
Pages (from-to)1677-1686
Number of pages10
JournalJournal of Chemical Physics
Volume92
Issue number3
Publication statusPublished - 1990

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coefficients
approximation
Potential energy surfaces
Angular momentum
Hot Temperature
quantum numbers
angular momentum
potential energy
energy
shift

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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title = "Reduced-dimensionality quantum calculations of the thermal rate coefficient for the Cl+HCl→ClH+Cl reaction: Comparison with centrifugal-sudden distorted wave, coupled channel hyperspherical, and experimental results",
abstract = "Reduced dimensionality (RD) cumulative reaction probabilities (CRPs) are reported for the Cl + HCl→ClH + Cl reaction using two semiempirical extended London-Eyring-Polanyi-Sato potential energy surfaces. Comparison is made with CRPs from centrifugal-sudden distorted wave (CSDW) calculations, and with accurate coupled channel hyperspherical (CCH) CRPs for total angular momentum quantum number J=0. Rotational and bending energy-shift approximations are applied to the CCH CRPs for J=0 to obtain approximate CRPs for J>0. A test of this approximation is made using CSDW partial wave CRPs. New expressions for the thermal rate coefficient are derived using these approximations. The rate coefficients calculated from RD and energy-shifted CCH CRPs are in excellent agreement with each other. They also agree well with the CSDW and experimental rate coefficients.",
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TY - JOUR

T1 - Reduced-dimensionality quantum calculations of the thermal rate coefficient for the Cl+HCl→ClH+Cl reaction

T2 - Comparison with centrifugal-sudden distorted wave, coupled channel hyperspherical, and experimental results

AU - Sun, Qiyan

AU - Bowman, Joel M.

AU - Schatz, George C

AU - Sharp, J. R.

AU - Connor, J. N L

PY - 1990

Y1 - 1990

N2 - Reduced dimensionality (RD) cumulative reaction probabilities (CRPs) are reported for the Cl + HCl→ClH + Cl reaction using two semiempirical extended London-Eyring-Polanyi-Sato potential energy surfaces. Comparison is made with CRPs from centrifugal-sudden distorted wave (CSDW) calculations, and with accurate coupled channel hyperspherical (CCH) CRPs for total angular momentum quantum number J=0. Rotational and bending energy-shift approximations are applied to the CCH CRPs for J=0 to obtain approximate CRPs for J>0. A test of this approximation is made using CSDW partial wave CRPs. New expressions for the thermal rate coefficient are derived using these approximations. The rate coefficients calculated from RD and energy-shifted CCH CRPs are in excellent agreement with each other. They also agree well with the CSDW and experimental rate coefficients.

AB - Reduced dimensionality (RD) cumulative reaction probabilities (CRPs) are reported for the Cl + HCl→ClH + Cl reaction using two semiempirical extended London-Eyring-Polanyi-Sato potential energy surfaces. Comparison is made with CRPs from centrifugal-sudden distorted wave (CSDW) calculations, and with accurate coupled channel hyperspherical (CCH) CRPs for total angular momentum quantum number J=0. Rotational and bending energy-shift approximations are applied to the CCH CRPs for J=0 to obtain approximate CRPs for J>0. A test of this approximation is made using CSDW partial wave CRPs. New expressions for the thermal rate coefficient are derived using these approximations. The rate coefficients calculated from RD and energy-shifted CCH CRPs are in excellent agreement with each other. They also agree well with the CSDW and experimental rate coefficients.

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