On the chemical enhancement in SERS

In Surface-enhanced Raman scattering (SERS), the Raman signal of a molecule adsorbed on a metal surface is enhanced by many orders of magnitude. This provides a "finger-print" of molecules which can be used in ultrasensitive sensing devises. Here we present a time-dependent density functional theory (TDDFT) study of the molecule-surface chemical coupling in SERS. A systematic study of the chemical enhancement (CHEM) of meta-and para-substituted pyridines interacting with a small silver cluster (Ag20) is presented. We find that the magnitude of chemical enhancement is governed to a large extent by the energy difference between the highest occupied energy level (HOMO) of the metal and the lowest unoccupied energy level (LUMO) of the molecule. A two-state approximation shows that the enhancement scales roughly as (ωX/ω¯e)4, where ω¯e is an average excitation energy between the HOMO of the metal and the LUMO of the molecule and wX the HOMO-LUMO gap of the free molecule. Furthermore, we demonstrate that it is ...