Weak predissociation of the EF, GK, and H 1σ g+ states of the H2 molecule by nonadiabatic coupling with the electronic ground state

Abstract

The energy shifts and widths generated in the vibrational levels of the EF, GK, and H 1Σg+ states of H2 by their nonadiabatic interactions with the electronic ground state have been calculated using ab initio wave functions. The shifts of the 44 quasibound vibronic levels of these excited states range from +0.02 to +1.00 cm -1. Along the EF progression the shifts are found to depend on vibrational kinetic energy in surprisingly good accord with the Van Vleck approximation. The calculated nonradiative decay probabilities range up to 3.3×106 s-1, and in one case the predissociation rate is as large as 39% of the radiative one. Experimental tests of these predictions are not yet available. © 1990 American Institute of Physics.