On the use of semiclassical dynamics in determining electronic spectra of Br2 in an Ar matrix

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Abstract
A semiclassical method to simulate the electronic absorption and emission spectra of Br2 in an Ar matrix is presented. The appropriate time correlation functions are evaluated in the Condon approximation using Gaussian wave packet dynamics. Several approximate methods are used to propagate the wave packet and their relative merits in obtaining high resolution spectra are discussed. The dynamics using a single Gaussian wave packet is inadequate for obtaining spectra in highly anharmonic systems, frequently encountered in condensed phase problems. Where possible, the results of the simulation are compared in detail with available experiments. The simulated electronic absorption spectra confirm the physical picture advanced by Bondebey and Brus. It is shown that from the spectral analysis of the emission spectra one can infer some features of the guest–host interaction when the guest is in the electronically excited state.