Temperature-dependent vibrational spectra and structure of liquid water from classical and quantum simulations with the MB-pol potential energy function.

Abstract

The structure of liquid water as a function of temperature is investigated through the modeling of infrared and Raman spectra along with structural order parameters calculated from classical and quantum molecular dynamics simulations with the MB-pol many-body potential energy function. The magnitude of nuclear quantum effects is also monitored by comparing the vibrational spectra obtained from classical and centroid molecular dynamics, both in intensities and peak positions. The observed changes in spectral activities are shown to reflect changes in the underlying structure of the hydrogen-bond network and are found to be particularly sensitive to many-body effects in the representation of the electrostatic interactions. Overall, good agreement is found with the experimental spectra, which provides further evidence for the accuracy of MB-pol in predicting the properties of water.