Accurate nonadiabatic couplings for H3: Application to predissociation

Abstract

We report the results of an ab initio calculation, using analytic techniques, of nonadiabatic couplings for H3 between the degenerate 2E′ ground state and the 2s(2A1′), 3s(2A1′) and 3p(2E′) Rydberg states. The calculations employed extensive correlated wave functions that accurately reproduced the energy levels of these states. We have used these couplings as input to a two-dimensional wave packet calculation of dissociation dynamics in order to predict the predissociation lifetimes and final state vibrational distributions produced by the predissociation. A significant isotope effect is found in the final vibrational distributions produced from H3 and D3 predissociation.