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首页> 外文期刊>journal of chemical physics >Test of variational transition state theory with a largehyphen;curvature tunneling approximation against accurate quantal reaction probabilities and rate coefficients for three collinear reactions with large reactionhyphen;path curvature: Cl+HCl, Cl+DCl, and Cl+MuCl
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Test of variational transition state theory with a largehyphen;curvature tunneling approximation against accurate quantal reaction probabilities and rate coefficients for three collinear reactions with large reactionhyphen;path curvature: Cl+HCl, Cl+DCl, and Cl+MuCl

机译：Test of variational transition state theory with a largehyphen;curvature tunneling approximation against accurate quantal reaction probabilities and rate coefficients for three collinear reactions with large reactionhyphen;path curvature: Cl+HCl, Cl+DCl, and Cl+MuCl

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The largehyphen;curvature groundhyphen;state model for the transmission coefficient of generalized transition state theory lsqb;presented in a previous paper by B. C. Garrett, D. G. Truhlar, A. F. Wagner, and T. H. Dunning, J. Chem. Phys. 78, 4400(1983)rsqb; is tested against accurate quantal calculations of the rate coefficients for collinear reactions with very large inertial effects, namely Cl+HClrarr;ClH+Cl, Cl+DClrarr;ClD+Cl, and Cl+MuClrarr;ClMu+Cl. The tests cover the temperature range 200ndash;2400 K. The accurate rate calculations are based on reaction probabilities obtained by a new numerical method for solving Schrouml;dingerrsquo;s equation in Delvesrsquo; coordinates. Improved canonical variational transition state theory predicts rate coefficients 5.0ndash;18 times smaller than those predicted by conventional transition state theory for the H transfer; for the D transfer, the ratio is 2.0ndash;3.4; and for Mu it is 22ndash;2.8times;107. The largehyphen;curvature model predicts transmission coefficients as large as 41, 8, and 206 for the H, D, and Muhyphen;transfer cases at 200 K, decreasing to 1.2, 1.1, and 1.4 at 2400 K. Despite the large effect of variationally optimizing the transition state location and the large size of the tunneling effect and the wide variation of both effects with temperature, improved canonical variational transition state theory with largehyphen;curvature groundhyphen;state transmission coefficients (ICVT/LCG) is accurate within a factor of 1.7 over a temperature range of a factor of 8, 300ndash;2400 K, for all three reactions. At 200 K, the ICVT/LCG model underestimates the rate coefficients, by factors of 2.3, 1.9, and 1.5 for H, D, and Mu, respectively.

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