Vibrational strong coupling in liquid water from cavity molecular dynamics

Abstract

We assess the cavity molecular dynamics method for the calculation of vibrational polariton spectra, using liquid water as a specific example. We begin by disputing a recent suggestion that nuclear quantum effects may lead to a broadening of polariton bands, finding instead that they merely result in anharmonic red shifts in the polariton frequencies. We go on to show that our simulated cavity spectra can be reproduced to graphical accuracy with a harmonic model that uses just the cavity-free spectrum and the geometry of the cavity as input. We end by showing that this harmonic model can be combined with the experimental cavity-free spectrum to give results in good agreement with optical cavity measurements. Since the input to our harmonic model is equivalent to the input to the transfer matrix method of applied optics, we conclude that cavity molecular dynamics cannot provide any more insight into the effect of vibrational strong coupling on the absorption spectrum than this transfer matrix method, which is already widely used by experimentalists to corroborate their cavity results.

arXiv comment10 pages, 5 figures

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• Fast quasi-centroid molecular dynamics for water and ice
• h-CMD: An efficient hybrid fast centroid and quasi-centroid molecular dynamics method for the simulation of vibrational spectra
• Semiclassical Dynamics in Wigner Phase Space I : Adiabatic Hybrid Wigner Dynamics