Chemical mechanism of surface-enhanced Raman scattering via charge transfer in fluorenone-Ag complex.

The intermolecular interaction between fluorenone (FN) and silver surfaces was investigated experimentally and theoretically. The structural, electronic and optical properties of the FN-Ag complex indicate that the carbonyl group O atom in FN molecules is the adsorbed position site to attach the silver substrate through the weak bond O…Ag. The analysis of vibrational modes and Raman activity of the largely enhanced Raman peaks using two FN-Ag4-x (x  =  l, s) complex models reveals that only the a1 vibrational modes with C 2v symmetry are selectively enhanced, from the point view of the change of dipole moment and polarizability induced by the interaction between FN and Ag4 substrate. Furthermore, the direct visualized evidence of the surface-enhanced Raman scattering (SERS) chemical enhancement mechanism for the FN-Ag complex is presented. The results reveal that only the intermolecular charge transfer with π-π transition characterization between FN and an Ag4 cluster facilitates the resonance Raman process and is directly responsible for chemical enhancement of Raman scattering of the FN-Ag complex.