Infrared-visible sum-frequency generation spectra of CO on Ni(100)

Infrared-visible sum-frequency generation (SFG) spectra of the stretching region of carbon monoxide adsorbed on Ni(100) are measured as a function of overlayer coverage and substrate temperature. The frequency and linewidth of the CO vibrational resonance in SFG have a similar dependence on coverage and temperature to that observed in linear absorption and emission spectroscopies. The lineshape of the SFG resonance, however, is influenced by the nonlinear response of the underlying metal surface. A simple model indicates that the nonresonant response of the substrate is out of phase with respect to that of the resonant CO response.