Combinational Vibration Modes in H(2)O/HDO/D(2)O Mixtures Detected Thanks to the Superior Sensitivity of Femtosecond Stimulated Raman Scattering

[Image: see text] Overtones and combinational modes frequently play essential roles in ultrafast vibrational energy relaxation in liquid water. However, these modes are very weak and often overlap with fundamental modes, particularly in isotopologues mixtures. We measured VV and HV Raman spectra of H(2)O and D(2)O mixtures with femtosecond stimulated Raman scattering (FSRS) and compared the results with calculated spectra. Specifically, we observed the mode at around 1850 cm(–1) and assigned it to H–O–D bend + rocking libration. Second, we found that the H–O–D bend overtone band and the OD stretch + rocking libration combination band contribute to the band located between 2850 and 3050 cm(–1). Furthermore, we assigned the broad band located between 4000 and 4200 cm(–1) to be composed of combinational modes of high-frequency OH stretching modes with predominantly twisting and rocking librations. These results should help in a proper interpretation of Raman spectra of aqueous systems as well as in the identification of vibrational relaxation pathways in isotopically diluted water.