Fourth-order coherent Raman spectroscopy of liquid-solid interfaces: near-surface phonons of TiO2 (110) in liquids.

The fourth-order coherent Raman response of a TiO2 (110) surface covered by HCl aqueous solution, neat octanol, acetic acid, or carbon tetrachloride layers is acquired. Four fourth-order optical responses were identified at 837-826, 452-448, 371-362, and 184-183 cm(-1) and assigned to near-surface phonons of TiO2. A third-order response produced in the bulk liquid layer was superimposed on the fourth-order response, when coherent vibrations are efficiently excited in the layer.