On the interrelation between nuclear dynamics and spectral line shapes in clusters

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Abstract
We analyzespectral absorption line shapes simulated using the molecular dynamicsspectral density method. We explore three classes of line shapes: (1) the region of the 0–0 S 0→S 1(ππ*) transition of perylene⋅Ar N clusters, (2) the Xe1 S 0→3 P 1 transition of XeAr N clusters, and (3) the photoelectron spectrum of the Li4F4 cluster in the valence region. These spectra represent examples for weak, unresolved, and extensive vibrational progressions, which have been analyzed and assigned. Employing a simplified model for the energy gap autocorrelation function allows for an understanding of the different behaviors and for a classification of the interrelation between nuclear dynamics and spectralline shapes. With decreasing the characteristic decay time of the transition dipole autocorrelation function, the line shape passes the limiting cases of the model in the order fast modulation limit→vibrational progression limit→slow modulation limit, with the vibrational progression limit extending the limiting cases of the Kubo stochastic model of line shapes. Some simple qualitative rules have been extracted to predict the overall character of a line shape.