Intramolecular dynamics. III. Theoretical studies of the CH overtone spectra for benzene

Abstract

The electronic states of the ionic excimer Ar^{+ +}₂ are calculated using ab initio multireference configuration interaction and effective core pseudopotentials. Among states dissociating into Ar+(2P)+Ar+(2P), all are found to be repulsive, except the ground state, which occurs to be quasibound near Re=4.1a0 with a well depth of >=230 cm^−1. All states originating from Ar++(3P,1D,1S)+Ar are bound with dissociation energies in the range 3200–4500 cm^−1 and equilibrium distances between 5.6a0 and 6a0. Simulation emission spectra from bound excited states are derived from the calculated potentials and the possible contribution of the Ar^{+ +}₂ ion to the third continuum fluorescence is discussed.