Theoretical surface-enhanced Raman spectra study of substituted benzenes: I. Density functional theoretical SERS modelling of benzene and benzonitrile

Abstract This paper reports a DFT modelling of SERS spectra for benzene and benzonitrile on the basis of a simple noncoordinate substrate–adsorbate model. Assignment of normal modes was obtained from internal force constants and potential energy distribution matrices and used to identify, according the SERS selection rules, the orientation of the optimized molecules on the metallic surface. Calculated band enhancements are in good agreement with experimental observations. The optimized geometry parameters of the molecule–Ag system, changes of HOMO–LUMO energies are discussed to give insight in the different SERS mechanisms for both molecules.