Vibrational strong coupling in liquid water from cavity molecular dynamics

被引:17
|
作者
Lieberherr, Annina Z. [1 ]
Furniss, Seth T. E. [1 ]
Lawrence, Joseph E. [2 ]
Manolopoulos, David E. [1 ]
机构
[1] Univ Oxford, Dept Chem, Phys & Theoret Chem Lab, South Parks Rd, Oxford OX1 3QZ, England
[2] Swiss Fed Inst Technol, Lab Phys Chem, CH-8093 Zurich, Switzerland
来源
JOURNAL OF CHEMICAL PHYSICS | 2023年 / 158卷 / 23期
关键词
INFRARED INTENSITIES; MECHANICS; CONSTANTS;
D O I
10.1063/5.0156808
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
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.
引用
收藏
页数:9
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