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

被引:96
作者
SUN, QY
BOWMAN, JM
SCHATZ, GC
SHARP, JR
CONNOR, JNL
机构
[1] ARGONNE NATL LAB, DIV CHEM, THEORET CHEM GRP, ARGONNE, IL 60439 USA
[2] UNIV MANCHESTER, DEPT CHEM, MANCHESTER M13 9PL, LANCS, ENGLAND
关键词
D O I
10.1063/1.458049
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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. © 1990 American Institute of Physics.
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页码:1677 / 1686
页数:10
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