Possibility of breakdown of overdamped and narrowing limits in low-frequency Raman spectra: phenomenological band-shape analysis using the multiple-random-telegraph model.

Abstract

Depolarized low-frequency Raman spectra of liquid water and heavy water are investigated from 266 K to 356 K. The reduced Raman spectra below 250 cm(-1) are reproduced by a superposition of one relaxation mode and two damped harmonic oscillator modes. The multiple-random-telegraph (MRT) model, which takes into account inertia and memory effects, is applied to analyze the relaxation component. Two damped harmonic oscillators around 50 cm(-1) and 180 cm(-1) are known as a bendinglike mode and a stretchinglike mode, respectively. It is found that the intensity of the bendinglike mode in water (heavy water) gradually decreases with increasing temperature, and finally vanishes above about 296 K (306 K). The relaxation time of the MRT model is interpreted as representing the averaged lifetime of the vibrating unit. At high temperature, the relaxation time becomes short, that is to say, the vibrating unit is quickly destroyed before the 50 cm(-1) mode is oscillating sufficiently. In the present analysis, the strongly disrupted oscillation cannot be distinguished from the relaxation mode which includes the inertia and memory effects. It is found that the low-frequency Raman spectrum of liquid water at high temperature is a good example demonstrating an application of the MRT model.