Electron detachment of hydrogen anion in collisions with hydrogen molecule studied by surface hopping classical trajectory calculations.

Abstract

We employ the on-the-fly surface hopping classical trajectory algorithm to study the electron detachment process in low-energy H- + H2 collisions. The ground-state and the first-excited-state Local Complex Potentials (LCPs) calculated by the generalized diatomics-in-molecule method are used for the full three-dimensional nonadiabatic nuclear dynamics. Two kinds of nonadiabatic effects are taken into account: discrete-discrete transitions and discrete-continuous transitions. Discrete-discrete nonadiabatic transition probabilities are calculated by means of the adiabatic-potential-based formula within the Landau-Zener model for each individual trajectory computed along real parts of the LCPs. Discrete-continuous (electron detachment) nonadiabatic transition probabilities are calculated via quasi-stationary widths which are related to the imaginary parts of the LCPs of both the electronic states of the H3- anion. Two mechanisms of the electron detachment process are treated and discussed: the direct mechanism based on quasi-stationarity of the ground state and the indirect mechanism based on both nonadiabatic transitions from the ground state to the first excited state and quasi-stationarity of the excited state. It is shown that the direct mechanism prevails at low collision energies, while the indirect mechanism makes a substantial contribution at relatively high collision energies, roughly higher than 5 eV. At collision energies higher than 2 eV, the electron detachment probability has rather high values and this affects noticeably other inelastic processes in these collisions. The electron detachment cross section in H- + H2 collisions is calculated for the collision energy range from 1 to 100 eV and a reasonable agreement with available experimental data is obtained.