Influence of Intermolecular Coupling on the Vibrational Spectrum of Water.

Raman multivariate curve resolution (Raman-MCR) spectra obtained from pure and isotopically dilute water are used to probe the influence of intermolecular resonance couplings on water OH and OD stretch band shapes and intensities, in the absence of intramolecular coupling. Intermolecular resonant coupling is found to broaden and red-shift the OH stretch band of water, in qualitative agreement with the predictions of Yang and Skinner. The influence of intermolecular coupling is found to increase with decreasing temperature, and to increase the Raman scattering cross section of the OH stretch, but decrease the OD stretch cross section. Moreover, we find that intermolecular coupling slightly perturbs the vibrational spectra of water molecules surrounding HOD.