We propose a cavity QED approach to describe light-matter interaction of an infrared cavity field with an anharmonic vibration of a single nonpolar molecule. Starting from a generic Morse oscillator potential with quantized nuclear motion, we derive a multilevel quantum Rabi model to study vibrational polaritons beyond the rotating-wave approximation. We analyze the spectrum of vibrational polaritons in detail and compare it with available experiments. For high excitation energies, the system exhibits a dense manifold of polariton level crossings and avoided crossings as the light-matter coupling strength and cavity frequency are tuned. We also analyze polariton eigenstates in nuclear coordinate space. We show that the bond length of a vibrational polariton at a given energy is never greater than the bond length of a Morse oscillator with the same energy. This type of polariton bond strengthening occurs at the expense of the creation of virtual infrared cavity photons and may have implications in chemical reactivity of polariton states.
Skip Nav Destination
Multi-level quantum Rabi model for anharmonic vibrational polaritons
Article navigation
14 October 2019
Research Article|
October 14 2019
Multi-level quantum Rabi model for anharmonic vibrational polaritons
Special Collection:
JCP Emerging Investigators Special Collection
Federico J. Hernández
;
Federico J. Hernández
1
Department of Physics, Universidad de Santiago de Chile
, Av. Ecuador, 3493 Santiago, Chile
Search for other works by this author on:
Felipe Herrera
Felipe Herrera
a)
1
Department of Physics, Universidad de Santiago de Chile
, Av. Ecuador, 3493 Santiago, Chile
2
Millennium Institute for Research in Optics MIRO
, Concepción, Chile
Search for other works by this author on:
a)
Electronic mail: [email protected]
Note: This paper is part of the JCP Emerging Investigators Special Collection.
J. Chem. Phys. 151, 144116 (2019)
Article history
Received:
July 24 2019
Accepted:
September 09 2019
Citation
Federico J. Hernández, Felipe Herrera; Multi-level quantum Rabi model for anharmonic vibrational polaritons. J. Chem. Phys. 14 October 2019; 151 (14): 144116. https://doi.org/10.1063/1.5121426
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Related Content
Polariton response in the presence of Brownian dissipation from molecular vibrations
J. Chem. Phys. (January 2021)
Effects of disorder on polaritonic and dark states in a cavity using the disordered Tavis–Cummings model
J. Chem. Phys. (May 2022)
A versatile platform for gas-phase molecular polaritonics
J. Chem. Phys. (October 2023)
Condensation of 2D exciton-polaritons in an open-access microcavity
J. Appl. Phys. (March 2022)