Near-resonant effects in the quantum dynamics of the H + H2 + → H2 + H+ charge transfer reaction and isotopic variants.

Abstract

The non-adiabatic quantum dynamics of the H + H2 + → H2 + H+ charge transfer reactions, and some isotopic variants, is studied with an accurate wave packet method. A recently developed 3 × 3 diabatic potential model is used, which is based on very accurate ab initio calculations and includes the long-range interactions for ground and excited states. It is found that for initial H2 +(v = 0), the quasi-degenerate H2(v' = 4) non-reactive charge transfer product is enhanced, producing an increase in the reaction probability and cross section. It becomes the dominant channel from collision energies above 0.2 eV, producing a ratio between v' = 4 and the rest of v's, which that increase up to 1 eV. The H + H2 + → H2 + + H exchange reaction channel is nearly negligible, while the reactive and non-reactive charge transfer reaction channels are of the same order, except that corresponding to H2(v' = 4), and the two charge transfer processes compete below 0.2 eV. This enhancement is expected to play an important vibrational and isotopic effect that needs to be evaluated. For the three proton case, the problem of the permutation symmetry is discussed when using reactant Jacobi coordinates.