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

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.

References in corpus (12)

• Perspective: How good is DFT for water?
• Competing quantum effects in the dynamics of a flexible water model
• How to remove the spurious resonances from ring polymer molecular dynamics
• On the accuracy of the MB-pol many-body potential for water: Interaction energies, vibrational frequencies, and classical thermodynamic and dynamical properties from clusters to liquid water and ice
• Accelerating the convergence of path integral dynamics with a generalized Langevin equation
• A simple and accurate algorithm for path integral molecular dynamics with the Langevin thermostat
• On the representation of many-body interactions in water
• A unified thermostat scheme for efficient configurational sampling for classical/quantum canonical ensembles via molecular dynamics
• Structure and Dynamics of the Instantaneous Water/Vapor Interface Revisited by Path-Integral and Ab-Initio Molecular Dynamics Simulations
• Water: one molecule, two surfaces, one mistake
• Stationary state distribution and efficiency analysis of the Langevin equation via real or virtual dynamics
• Path Integral Molecular Dynamics for Exact Quantum Statistics of Multi-Electronic-State Systems

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