Novel surface vibrational spectroscopy: infrared-infrared-visible sum-frequency generation.

A novel type of surface vibrational sum-frequency generation spectroscopy is presented that enables a highly specific measurement of the coupling of molecules on surfaces. With this doubly vibrationally resonant technique, two-dimensional vibrational spectroscopy of molecules on surfaces becomes possible. The technique is demonstrated for the C-O stretch vibration of CO on a ruthenium (001) surface.