Issue 22, 2020

Vibrational mode frequency correction of liquid water in density functional theory molecular dynamics simulations with van der Waals correction

Abstract

The frequencies and spectral lineshapes of the stretch and bending modes of water provide invaluable information on the microscopic structures of water in aqueous solutions and at the water/solid interfaces. Density functional theory molecular dynamics (DFT-MD) simulation has been used not only for predicting the properties of water but also for interpreting the vibrational spectra of water. Since the accuracy of the DFT-MD simulations relies on the choice of the exchange–correlation functionals and dispersion correction schemes employed, the predicted vibrational spectra at different levels of DFT theory differ significantly, prohibiting precise comparison of simulated spectra with experimental data. Here, we simulate the vibrational density of states for liquid heavy water based on various DFT-MD trajectories. We find that DFT-MD simulations tend to predict excessive inhomogeneous broadening for the stretch mode of water. Furthermore, we develop a frequency correction scheme for the stretch and bending modes of liquid water, which substantially improves the prediction of the vibrational spectra.

Graphical abstract: Vibrational mode frequency correction of liquid water in density functional theory molecular dynamics simulations with van der Waals correction

Supplementary files

Article information

Article type
Paper
Submitted
24 Nov 2019
Accepted
22 Mai 2020
First published
22 Mai 2020
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2020,22, 12785-12793

Vibrational mode frequency correction of liquid water in density functional theory molecular dynamics simulations with van der Waals correction

K. Zhong, C. Yu, M. Dodia, M. Bonn, Y. Nagata and T. Ohto, Phys. Chem. Chem. Phys., 2020, 22, 12785 DOI: 10.1039/C9CP06335H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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