Selective Chemical Raman Enhancement for Organic Adsorbates at Metal Surfaces*

It has long been observed that in surface enhanced Raman spectroscopy (SERS) relative mode intensities differ from gas- and solution-phase data, which obscures understanding of SERS in general. Using first-principles methods, we examine how chemisorption affects Raman scattering of molecules on metal surfaces relative to gas-phase, and provide a quantitative description of this effect. Calculated Raman spectra for benzene thiol bound at different sites on Au(111) show that chemical enhancement arises from the mode dependent electron-phonon coupling of the metal-molecule interface. Site-dependent enhancements are explained correlated to interfacial electronic structure. Comparison to experiments suggests affinity of benzene thiol for bridge sites on Au(111) surfaces.