Pre-resonance effects in deep UV Raman spectra of normal and deuterated water.

We have investigated the shape of the OH/OD stretching Raman band of water as a function of the excitation wavelength in the deep UV region (200-266 nm). By analyzing the spectral profiles, we highlighted selective pre-resonance effects in the high wavenumber component of the OH/OD stretching band, associated to distorted H-bonded water configurations. A van't Hoff treatment of the temperature-dependent Raman spectra provides an estimate of the thermal energy associated to the change from ordered (ice-like) to disordered configurations that agrees with values obtained by related methods based on a two-state model of water. These results open the possibility of exploiting the observed pre-resonance deep-UV signal enhancement to investigate H-bonding properties in aqueous media.