Interrogation of vibrational structure and line broadening of liquid water by Raman-induced Kerr effect measurements within the multimode Brownian oscillator model

The method used to deduce the spectral density distribution of intermolecular and intramolecular (vibrational) degrees of freedom in the liquid state from optical heterodyne detected optical (Raman-induced) Kerr effect (OHD-RIKE) measurements is reexamined within a multimode Brownian oscillator model, The ramifications of nonlinear coupling of the nuclear degrees of freedom to the medium polarizability are explored for discrimination between ''homogeneous'' and ''inhomogeneous'' contributions to the vibrational spectral density, Under physically reasonable assumptions, an estimation of the homogeneous contribution to the vibrational line shape can be made from the OHD-RIKE observable (if nonlinear coupling is nonnegligible). The model is developed generally, and calculations are applied specifically to temperature-dependent OHD-RIKE measurements of liquid water. The results indicate that the line broadening in the low-frequency vibrational distribution due to the hydrogen-bonded network structure of liquid water is mostly inhomogeneous, with an effective homogeneous relaxation time of 350 fs at 24 degrees C.