TY - JOUR
T1 - Quantum Simulations of Vibrational Strong Coupling via Path Integrals
AU - Li, Tao E.
AU - Nitzan, Abraham
AU - Hammes-Schiffer, Sharon
AU - Subotnik, Joseph E.
N1 - Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.
PY - 2022/5/5
Y1 - 2022/5/5
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85129302510&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.2c00613
DO - 10.1021/acs.jpclett.2c00613
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C2 - 35471100
AN - SCOPUS:85129302510
SN - 1948-7185
VL - 13
SP - 3890
EP - 3895
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 17
ER -