Lambda-type sharp rise in the widths of Raman and infra-red line shape near the Widom line in super-critical water above its gas-liquid critical temperature

TL;DR

This study investigates the lambda-type divergence in Raman and infra-red line widths near the Widom line in super-critical water, using simulations and quantum calculations to reveal a sharp increase in vibrational relaxation rates.

Contribution

It demonstrates the occurrence of a lambda-type anomaly in super-critical water's vibrational linewidths across the Widom line through simulations and quantum chemical analysis.

Findings

Sharp rise in vibrational relaxation rate across the Widom line

Anomaly due to increased mean square frequency fluctuation

No evidence of dynamical critical slowing down

Abstract

A lambda-type divergent rise of Raman linewidth of liquid nitrogen near its critical temperature has been a subject of many discussions in the past[1-5]. Here we explore the possibility of such an anomaly in infra-red and Raman spectroscopy of super-critical water (SCW) by varying the density across the Widom line just above its critical temperature. Vibrational phase relaxation is expected to be a sensitive probe of fluid dynamics. We carry out computer simulations of two different model potentials (SPC/E and TIP4P/2005) to obtain the necessary time correlation functions. An additional feature of this work is a quantum chemical calculation of the anharmonicity parameter that largely controls frequency fluctuations. We find a sharp rise in the vibrational relaxation rate (or the line widths) for both the models as we travel across the Widom line. The rise is noticeably less sharp in water than in nitrogen. We attribute this difference to the faster relaxation rate in water. We demonstrate that the anomalous rise is due to sharp increase in the mean square frequency fluctuation and not due to any dynamical critical slowing down because the time constant of the normalized frequency-frequency time correlation functions show lack of any noticeable change as we move across the Widom line. We present an explanation of the observed results using the mode coupling theory of liquid dynamics.