TY - JOUR

T1 - Test of variational transition state theory against accurate quantal results for a reaction with very large reaction-path curvature and a low barrier

AU - Truhlar, Donald G.

AU - Garrett, Bruce C.

AU - Hipes, Paul G.

AU - Kuppermann, Aron

PY - 1984

Y1 - 1984

N2 - We present three sets of calculations for the thermal rate constants of the collinear reaction I+HI→IH+I: accurate quantum mechanics, conventional transition state theory (TST), and variational transition state theory (VTST). This reaction differs from previous test cases in that it has very large reaction-path curvature but hardly any tunneling. TST overestimates the accurate results by factors of 2×1010, 2×104, 57, and 19 at 40, 100, 300, and 1000 K, respectively. At these same four temperatures the ratios of the VTST results to the accurate quantal ones are 0.3, 0.8, 1.1, and 1.4, respectively. We conclude that the variational transition states are meaningful, even though they are computed from a reaction-path Hamiltonian with large curvature, which is the most questionable case.

AB - We present three sets of calculations for the thermal rate constants of the collinear reaction I+HI→IH+I: accurate quantum mechanics, conventional transition state theory (TST), and variational transition state theory (VTST). This reaction differs from previous test cases in that it has very large reaction-path curvature but hardly any tunneling. TST overestimates the accurate results by factors of 2×1010, 2×104, 57, and 19 at 40, 100, 300, and 1000 K, respectively. At these same four temperatures the ratios of the VTST results to the accurate quantal ones are 0.3, 0.8, 1.1, and 1.4, respectively. We conclude that the variational transition states are meaningful, even though they are computed from a reaction-path Hamiltonian with large curvature, which is the most questionable case.

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U2 - 10.1063/1.448082

DO - 10.1063/1.448082

M3 - Article

AN - SCOPUS:0001247977

SN - 0021-9606

VL - 81

SP - 3542

EP - 3545

JO - The Journal of chemical physics

JF - The Journal of chemical physics

IS - 8

ER -