Experimental Evidence of Fermi Resonances in Isotopically Dilute Water from Ultrafast Broadband IR Spectroscopy

Abstract

The vibrational dynamics of liquid water, which result from a complex interplay between internal molecular vibrations and the fluctuating hydrogen bond network, are fundamental to many physicochemical and biological processes. Using a new ultrafast broadband mid-infrared light source with over 2000 cm(-1) of bandwidth, we performed ultrafast time-resolved infrared spectroscopy to study the vibrational couplings and relaxation dynamics of the stretching and bending vibrations of the mixed isotopologue, HOD, in D2O. Analysis of cross-peaks and induced absorptions in the two-dimensional infrared spectrum and transient absorption spectrum shows that the hydroxyl stretch of HOD is coupled to the HOD bending mode via Fermi resonance, with a 70° angle between their transition dipole moments. We see that HOD is also anharmonically coupled to the D2O solvent modes. From transient absorption spectra, we conclude that vibrational relaxation occurs through a number of paths. The strongly hydrogen-bonded OH oscillators have the highest propensity to relax through the bending mode, while the weakly hydrogen bonded oscillators relax through other modes.