Critical role of quantum dynamical effects in the Raman spectroscopy of liquid water

TL;DR

This study employs quantum dynamical simulations to elucidate the atomistic origins of key features in the Raman spectra of liquid water, highlighting the importance of quantum effects in reproducing experimental spectral peaks.

Contribution

It introduces a semiclassical quantum dynamical approach using an ab initio polarizable model to accurately simulate liquid water's Raman spectra, revealing the critical role of quantum effects.

Findings

Quantum effects are essential for reproducing key Raman spectral peaks.

The intermediate spectral region peaks result from stretching and bending mode interplay.

Different vibrational modes contribute distinctly to isotropic and anisotropic spectra.

Abstract

Understanding the Raman spectroscopy at the atomistic level is important for the elucidation of dynamical processes in liquid water. Because the polarizability (or its time derivative) is often a highly nonlinear function of coordinates or/and momenta, we employ the linearized semiclassical initial value representation for quantum dynamical simulations of liquid water (and heavy water) under ambient conditions based on an ab initio based, flexible, polarizable model (the POLI2VS force field). It is shown that quantum dynamical effects play a critical role in reproducing the peaks in the intermediate region between the librational and bending bands, those between the bending and stretching bands, and the double-peak in the stretching band in the experimental isotropic Raman spectrum. In contrast, quantum dynamical effects are important but less decisive in the anisotropic Raman spectrum. By selectively freezing either the intramolecular O-H stretching or H-O-H bending mode, we demonstrate that the peak in the intermediate region (2000-2400 cm-1) of the isotropic Raman spectrum arises from the interplay of the stretching and bending motions while a substantial part of the peak in the same intermediate region of the anisotropic Raman spectrum may be attributed to the combined motion of the bending and librational modes.