Determination of the degree of charge-transfer contributions to surface-enhanced Raman spectroscopy

We explore the application of a previously suggested formula for determining the degree of charge transfer in surface-enhanced Raman scattering (SERS). SERS is often described as a phenomenon which obtains its enhancement from three major sources, namely the surface plasmon resonance, charge-transfer resonances as well as possible molecular resonances. At any chosen excitation wavelength, it is possible to obtain contributions from several sources and this has led to considerable confusion. The formula for the degree of charge transfer enables one to separate these effects, but it requires that spectra be obtained either at two or more different excitation wavelengths or as a function of applied potential. We apply this formula to several examples, which display rather large charge-transfer contributions to the spectrum. These are p-aminothiophenol (PATP), tetracyano-ethylene (TCNE) and piperidine. In PATP we can show that several lines of the same symmetry give the same degree of charge transfer. In TCNE we are able to identify the charge-transfer transition, which contributes to the effect, and are able to independently determine the degree of charge transfer by wavenumber shifts. This enables a comparison of the two techniques of measurement. In piperidine, we present an example of molecule to metal charge transfer and show that our definition of charge transfer is independent of direction.