PNNL

Abstract

We employ the atom-centered density-matrix propagation method to illustrate how time-dependent structural and conformational changes affect the electronic structure and derived spectroscopic properties of a prototypical finite metal cluster-bound p-conjugated organic, namely the Ag7-benzenethiol complex. We find that the calculated spectroscopic properties are dictated by large amplitude motion which controls the coupling between the aromatic ring of the molecule and the metal cluster. The simulated vibrational spectra of Ag7-benzenethiol are in accord with previous experiments which probe Raman scattering from benzenethiol adsorbed on silver surfaces.