Raman scattering from molecular conduction junctions: Charge transfer mechanism

We present a model for the charge transfer contribution to surface-enhanced Raman spectroscopy (SERS) in a molecular junction. The model is a generalization of the equilibrium scheme for SERS of a molecule adsorbed on a metal surface [B. N. J. Persson. Chem. Phys. Lett. 82, 561 (1981)]. We extend the same physical consideration to a nonequilibrium situation in a biased molecular junction and to nonzero temperatures. Two approaches are considered and compared: a semiclassical approach appropriate for nonresonance Raman scattering, and a quantum approach based on the nonequilibrium Green’s function method. Nonequilibrium effects on this contribution to SERS are demonstrated with numerical examples. It is shown that the semiclassical approach provides an excellent approximation to the full quantum calculation as long as the molecular electronic state is outside the Fermi window, that is, as long as the field-induced charge transfer is small.