Quantum collinear reaction probabilities for vibrationally excited reactants : F+H2(v≤2)→FH(v′≤5)+H

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Abstract
Quantum mechanical reaction probabilities are reported for the collinear reaction F+H2(v)→FH(v′)+H in an energy range where two or three vibrational H2 states v are open. Rotated Morse-cubic spline representations of the extended LEPS surfaces Muckerman I and V, and an adaptation of the BOPS SCFCI surface have been used. The scattering is dominated by resonances. A detailed investigation of the different kinds of resonance behaviour is presented. For the two LEPS surfaces, overall features of the reaction probability curves can be correlated qualitatively in a one-to-one manner. Differences between the BOPS and LEPS reaction probabilities are more pronounced for v=1 than for v=0. For all surfaces, effects of vibrational excitation show a much more systematic behaviour in terms of the reverse reaction than for the forward reaction. A multi-step mechanism is deduced for the reaction, and an attempt is made to give an interpretation in terms of physical concepts including centrifugal effects, Franck-Condon transitions and quasibound states. No obvious simple trends emerge from a surprisal analysis. Most surprisal plots are markedly non-linear in the energy range considered.