Vibronic coupling and selectivity of vibrational excitation in the negative ion resonances of ozone

Abstract

Listen

Translate article

A recent experimental paper reported two shape resonances in electron impact on ozone, A 1 and B 2, both causing vibrational excitation with a distinct pattern of selectivity. The present Letter attempts to rationalize this selectivity using approximate potential curves, calculated for the A 1 and B 2 resonances by adding the SCF energy of neutral ozone to electron attachment energies calculated from ab initio virtual orbital energies using the Koopmans' theorem and an empirical scaling relation. The slopes of the curves explain the efficient excitation of the symmetric stretch by both resonances and the lack of the bending excitation by the B 2 resonance. The A 1 and B 2 resonances are strongly coupled by the b 2 antisymmetric stretch vibration, causing a double minimum on the lower surface. Nonadiabatic effects caused by the strong vibronic coupling explain the observed excitation of the antisymmetric stretch vibration.