Anharmonicity and tunneling effects in revisited vibrational O(1s) photoelectron spectrum of water gas phase

Abstract

The authors have revisited the description of the core-hole ionization dynamics of the oxygen atom in water by re-exploiting the high-resolution, vibrationally resolved, XPS photoelectron spectrum of gas phase at the O(1s) edge. The agreement between theory and experiments is mainly controlled by (i) the description of the tunneling behavior near the barrier top (linear H-O-H conformation) of wave functions with high vibrational quanta, and (ii) the relative displacement of the potential-energy minimum of the O(1s) final state with respect to the ground state one. Accurate change in bond angle between the neutral and core-ionized states is essential to account for the Franck-Condon factors. The O(1s) photoelectron spectrum of water is well reproduced by the molecular ab initio calculations based on density functional theory and Franck-Condon factors calculations in a double-well (2 x W) simulation of the bending motion.