  Using a combination of first-principles theory and experiments, we provide a
quantitative explanation for chemical contributions to surface-enhanced Raman
spectroscopy for a well-studied organic molecule, benzene thiol, chemisorbed on
planar Au(111) surfaces. With density functional theory calculations of the
static Raman tensor, we demonstrate and quantify a strong mode-dependent
modification of benzene thiol Raman spectra by Au substrates. Raman active
modes with the largest enhancements result from stronger contributions from Au
to their electron-vibron coupling, as quantified through a deformation
potential, a well-defined property of each vibrational mode. A straightforward
and general analysis is introduced that allows extraction of chemical
enhancement from experiments for specific vibrational modes; measured values
are in excellent agreement with our calculations.
