TY - JOUR

T1 - Test of variational transition state theory with a large-curvature tunneling approximation against accurate quantal reaction probabilities and rate coefficients for three collinear reactions with large reaction-path curvature

T2 - Cl+HCl, Cl+DCl, and Cl+MuCl

AU - Bondi, D. K.

AU - Connor, J. N.L.

AU - Garrett, Bruce C.

AU - Truhlar, Donald G.

PY - 1982

Y1 - 1982

N2 - The large-curvature ground-state model for the transmission coefficient of generalized transition state theory [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)] is tested against accurate quantal calculations of the rate coefficients for collinear reactions with very large inertial effects, namely Cl+HCl→ClH+Cl, Cl+DCl-→ClD+Cl, and Cl+MuCl→ClMu+Cl. The tests cover the temperature range 200-2400 K. The accurate rate calculations are based on reaction probabilities obtained by a new numerical method for solving Schrödinger's equation in Delves' coordinates. Improved canonical variational transition state theory predicts rate coefficients 5.0-18 times smaller than those predicted by conventional transition state theory for the H transfer; for the D transfer, the ratio is 2.0-3.4; and for Mu it is 22-2.8 × 107. The large-curvature model predicts transmission coefficients as large as 41, 8, and 206 for the H, D, and Mu-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 large-curvature ground-state transmission coefficients (ICVT/LCG) is accurate within a factor of 1.7 over a temperature range of a factor of 8, 300-2400 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.

AB - The large-curvature ground-state model for the transmission coefficient of generalized transition state theory [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)] is tested against accurate quantal calculations of the rate coefficients for collinear reactions with very large inertial effects, namely Cl+HCl→ClH+Cl, Cl+DCl-→ClD+Cl, and Cl+MuCl→ClMu+Cl. The tests cover the temperature range 200-2400 K. The accurate rate calculations are based on reaction probabilities obtained by a new numerical method for solving Schrödinger's equation in Delves' coordinates. Improved canonical variational transition state theory predicts rate coefficients 5.0-18 times smaller than those predicted by conventional transition state theory for the H transfer; for the D transfer, the ratio is 2.0-3.4; and for Mu it is 22-2.8 × 107. The large-curvature model predicts transmission coefficients as large as 41, 8, and 206 for the H, D, and Mu-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 large-curvature ground-state transmission coefficients (ICVT/LCG) is accurate within a factor of 1.7 over a temperature range of a factor of 8, 300-2400 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.

UR - http://www.scopus.com/inward/record.url?scp=36749108620&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=36749108620&partnerID=8YFLogxK

U2 - 10.1063/1.444613

DO - 10.1063/1.444613

M3 - Article

AN - SCOPUS:36749108620

VL - 78

SP - 5981

EP - 5989

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 10

ER -