Theoretical study of the time-resolved photoelectron spectrum of Na₂F: effects of thermal initial conditions

Abstract.

The excited state dynamics of the Na₂F cluster initiated by a femtosecond laser pulse is studied considering a thermally excited initial sample. Within a pump-probe set-up, the time-dependent photoelectron spectrum is calculated, which is shown to be a sensitive tool to study intramolecular motion of the cluster. Temperature effects are taken into account through thermal averaging over the time-dependent spectra obtained from different initial vibrational states of the cluster. The nuclear motion upon laser excitation is described by full-dimensional quantum wavepacket propagation using explicit, realistic pump and probe pulses. The characteristic features of the time-resolved photoelectron spectra of the Na₂F cluster, identified as due to periodic bending motion of the cluster as well as to the excitation of the stretching mode, are found to be robust against increasing vibrational temperature of the cluster beam. This finding is important for possible future experiments.