PNNL

Abstract

We compute the Raman spectra of 1,3-propanedithiol (PDT) in the gas phase, in methanol, linked either to the face or vertex of a finite tetrahedral Ag20 cluster, and linking two Ag20 clusters using tools of density functional theory. The calculated normal mode-dependent molecular polarizability derivative tensors are employed to simulate single molecule surface-enhanced Raman (SERS) spectra. This is achieved by rotating the polarizability tensors of an individual molecule with respect to explicitly defined vector components of the incident and scattered radiation. Our results provide a basis for understanding commonly observed phenomena in single molecule SERS spectroscopy.