On the potential surface dependence of the H + F 2 reaction. I. Quantum mechanical and information theoretic investigations for various extended LEPS-surfaces

Abstract

Effects of potential surface variations for the H + F 2 (ν = O) → HF + F reaction have been investigated by a combination of collinear quantum calculations and an information theoretic 1D to 3D transformation. First collinear quantum calculations using the state path sum method have been performed for five extended LEPS surfaces with different combinations of Sato parameters. Total reaction probabilities at E trans = 0.109 eV increase with decreasing barrier height. The average vibrational product excitation (ƒ ν′) is found to be a linear function of the attractivity index α ⊥. The collinear vibrational distributions have been subjected to an information theoretic 1D to 3D transformation. Resulting 3D vibrational product distributions show approximately the same breadth for all surfaces, with (ƒ ν′) again linearly related to α ⊥. The breadth of the calculated distributions is narrower than the experimental one. Deviations from experiment, and the problem of selecting an “optimal” LEPS surface, are discussed. It is argued that the deviations might stem from a failure of the LEPS surfaces to account for some distinctive non-collinear reactive collisions.