Theoretical study of the electronic nonadiabatic transitions in the photoelectron spectroscopy of F<inf>2</inf>O

Abstract

The photoelectron spectrum of F2O pertaining to ionizations to the ground (X̃2B1) and low-lying excited electronic states (Ã2B2, B̃2A1, and C̃2A2) of F2O+ is investigated theoretically. The near equilibrium potential energy surfaces of the ground electronic state (X̃2B1) of F2O and the mentioned ground and excited electronic states of F2O+ reported by Wang et al. (J. Chem. Phys. 2001, 114, 10682) for the C2v configuration are extended for the Cs geometry assuming a harmonic vibration along the asymmetric stretching mode. The vibronic interactions between the Ã2B2 and B̃2A 1 electronic states of F2O+ are treated within a linear coupling approach, and the strength of the vibronic coupling parameter is calculated by an ab initio method. The nuclear dynamics is simulated by both time-independent quantum mechanical and time-dependent wave packet approaches. Although the first photoelectron band exhibits resolved vibrational progression along the symmetric stretching mode, the second one is highly overlapping. The latter is attributed to the nonadiabatic interactions among the energetically close Ã2B2, B̃2A1, and C̃2A2 electronic states of F2O +. The theoretical findings are in good accord with the available experimental results. © 2006 American Chemical Society.