Quantum Simulations of Vibrational Strong Coupling via Path Integrals

Tao E. Li*, Abraham Nitzan, Sharon Hammes-Schiffer, Joseph E. Subotnik

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review


A quantum simulation of vibrational strong coupling (VSC) in the collective regime via thermostated ring-polymer molecular dynamics (TRPMD) is reported. For a collection of liquid-phase water molecules resonantly coupled to a single lossless cavity mode, the simulation shows that as compared with a fully classical calculation, the inclusion of nuclear and photonic quantum effects does not lead to a change in the Rabi splitting but does broaden polaritonic line widths roughly by a factor of 2. Moreover, under thermal equilibrium, both quantum and classical simulations predict that the static dielectric constant of liquid water is largely unchanged inside vs outside the cavity. This result disagrees with a recent experiment demonstrating that the static dielectric constant of liquid water can be resonantly enhanced under VSC, suggesting either limitations of our approach or perhaps other experimental factors that have not yet been explored.

Original languageEnglish
Pages (from-to)3890-3895
Number of pages6
JournalJournal of Physical Chemistry Letters
Issue number17
StatePublished - 5 May 2022


FundersFunder number
National Science FoundationCHE1953701
U.S. Department of Energy
Air Force Office of Scientific ResearchFA9550-18-1-0134
Office of Science
Basic Energy Sciences
Chemical Sciences, Geosciences, and Biosciences DivisionDE-SC0019397


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