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The validity of transition state theory is examined for the bimolecular reaction of Li+HF→LiF+H. Accurate three-dimensional quantum scattering theory calculations of the cumulative reaction probability are reported for energies ranging from threshold (0.255 eV) up to 0.600 eV and a total angular momentum J of 0. Transition state theory estimates of the effect of both the entrance and exit channels on the cumulative reaction probability are reported for the same energy range and J value. The transition state theory results are found to provide an accurate description of the smoothed energy dependence of the cumulative reaction probabilities with a maximum disagreement between the two calculations of about 25% arising at the highest energy considered of 0.6 eV. [ABSTRACT FROM AUTHOR]

Accurate 3D coupled channel calculations for total angular momentum J=0 for the reaction F+H2→HF+H using a realistic potential energy surface are analyzed. The reactive scattering is formulated using the hyperspherical (APH) coordinates of Pack and Parker. The adiabatic basis functions are generated quite efficiently using the discrete variable representation method. Reaction probabilities for relative collision energies of up to 17.4 kcal/mol are presented. To aid in the interpretation of the resonances and quantum structure observed in the calculated reaction probabilities, we analyze the phases of the S matrix transition elements, Argand diagrams, time delays and eigenlifetimes of the collision lifetime matrix. Collinear (1D) and reduced dimensional 3D bending corrected rotating linear model (BCRLM) calculations are presented and compared with the accurate 3D calculations. [ABSTRACT FROM AUTHOR]