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Which quantum statistics-classical dynamics method is best for water?

Accepted version
Peer-reviewed

Type

Article

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Authors

Benson, Raz L 
Trenins, George 
Althorpe, Stuart C 

Abstract

There are a variety of methods for including nuclear quantum effects in dynamics simulations by combining quantum Boltzmann statistics with classical dynamics. Among them are thermostatted ring-polymer molecular dynamics (TRPMD), centroid molecular dynamics (CMD), quasi-centroid molecular dynamics (QCMD), and the linearised semi-classical initial value representation (LSC-IVR). Here we make a systematic comparison of these methods by calculating the infrared spectrum of water in the gas phase, and in the liquid and ice phases (using the q-TIP4P/F model potential). Some of these results are taken from previous work, and some of them are new (including the LSC-IVR calculations for ice, and extensions of all the spectra into the near-infrared region dominated by overtone and combination bands). Our results suggest that QCMD is the best method for reproducing fundamental transitions in the spectrum, and that LSC-IVR gives the best overall description of the spectrum (albeit with large errors in the bend fundamental band caused by zero-point-energy leakage). The TRPMD method gives damped spectra that line up with the QCMD spectra, and is by far the cheapest method.

Description

Keywords

34 Chemical Sciences, 3406 Physical Chemistry

Journal Title

Faraday Discuss

Conference Name

Journal ISSN

1359-6640
1364-5498

Volume Title

221

Publisher

Royal Society of Chemistry (RSC)

Rights

All rights reserved
Sponsorship
EPSRC (1942965)