Effect of Initial Vibrational-State Excitation on Subfemtosecond Photodynamics of Water.

Abstract

We discuss the effect of initial vibrational-state excitation on the subfemtosecond photodynamics of water. Photoelectron spectra of Franck-Condon ionization to the (2)B1 state of the H2O(+) (D2O(+)) from the ground and several vibrationally excited states of the neutral are reported. Also calculated are ratios of the high-order harmonic generation (HHG) signals as a function of time for each initial vibrational state of the neutral molecule as predicted from the ratios of the square of the autocorrelation functions for D2O(+) and H2O(+). They reveal maxima as a function of time for each vibrational state of the neutral molecule. In turn, the HHG signals are found to be enhanced with vibrational excitation, with the calculated expectation values of the bond lengths and bond angle revealing quasiperiodic oscillations in time for all initial vibrational states of the neutral species. Although the bond lengths show only a marginal increase, the bond angle is found to be enhanced markedly by vibrational excitation, this being therefore responsible for the observed rise in the HHG signal.