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The electromagnetic field in an optical cavity can dramatically modify and even control chemical reactivity via vibrational strong coupling (VSC). Since the typical vibration and cavity frequencies are considerably higher than thermal…

Quantum Physics · Physics 2021-09-29 Peiyun Yang , Jianshu Cao

We present a microscopic theory that aims to explain the vibrational strong coupling (VSC) modified reaction rate constant. The analytic theory is based on a mechanistic conjecture that cavity modes promote the transition from the ground…

Quantum Physics · Physics 2023-05-16 Wenxiang Ying , Michael A. D. Taylor , Pengfei Huo

Recent experiments suggest that vibrational strong coupling (VSC) may significantly modify ground-state chemical reactions and their rates even without external pumping. The intrinsic mechanism of this "vacuum-field catalysis" remains…

Chemical Physics · Physics 2020-06-17 Tao E. Li , Abraham Nitzan , Joseph E. Subotnik

In this paper we develop quantum dynamical methods capable of treating the dynamics of chemically reacting systems in an optical cavity in the vibrationally strong-coupling (VSC) limit at finite temperatures and in the presence of a…

Quantum Physics · Physics 2025-02-11 Lachlan P. Lindoy , Arkajit Mandal , David R. Reichman

For a small fraction of hot CO2 molecules immersed in a liquid-phase CO2 thermal bath, classical cavity molecular dynamics simulations show that forming collective vibrational strong coupling (VSC) between the C=O asymmetric stretch of CO2…

Chemical Physics · Physics 2021-05-11 Tao E. Li , Abraham Nitzan , Joseph E. Subotnik

Vibrational strong coupling (VSC) provides a novel means to modify chemical reactions and energy transfer pathways. To efficiently model chemical dynamics under VSC in the collective regime, herein a hybrid quantum mechanical/molecular…

Chemical Physics · Physics 2022-12-29 Tao E. Li , Sharon Hammes-Schiffer

Recent experiments have demonstrated that vibrational strong coupling (VSC) between molecular vibrations and the optical cavity field can modify vibrational energy transfer (VET) processes in molecular systems. However, the underlying…

Chemical Physics · Physics 2024-11-25 Qi Yu , Dong H. Zhang , Joel M. Bowman

In vibrational strong coupling (VSC), molecular vibrations strongly interact with the modes of an optical cavity to form hybrid light-matter states known as vibrational polaritons. Experiments show that the kinetics of thermally activated…

Quantum Physics · Physics 2021-05-04 Matthew Du , Jorge A. Campos-Gonzalez-Angulo , Joel Yuen-Zhou

In this thesis, we use classical, semi-classical and quantum-mechanical methods to simulate chemical reaction dynamics inside of an optical cavity. Within such a cavity, by selectively coupling vibrational modes of the reactants to the…

Chemical Physics · Physics 2024-02-08 Andrew C. Hunt

Under vibrational strong coupling (VSC), the formation of molecular polaritons may significantly modify the photo-induced or thermal properties of molecules. In an effort to understand these intriguing modifications, both experimental and…

Chemical Physics · Physics 2022-04-07 Tao E. Li , Abraham Nitzan , Joseph E. Subotnik

Recent advances in polaritonic chemistry suggest that chemical reactions can be controlled via collective vibrational strong coupling (VSC) in a cavity. In this fully analytical work, we demonstrate that the collective vibrations of a…

Quantum Physics · Physics 2025-04-15 Vasil Rokaj , Ilia Tutunnikov , H. R. Sadeghpour

In the regime of ensemble vibrational strong coupling (VSC), a macroscopic number $N$ of molecular transitions couple to each resonant cavity mode, yielding two hybrid light-matter (polariton) modes, and a reservoir of $N-1$ dark states…

Chemical Physics · Physics 2020-04-03 Jorge Campos-Gonzalez-Angulo , Raphael F. Ribeiro , Joel Yuen-Zhou

We study the bimolecular nucleophilic substitution (S$_\mathrm{N}$2) reaction of 1-phenyl-2-trimethylsilylacetylene (PTA) under vibrational strong coupling (VSC) from the perspective of high-level ab initio quantum and polaritonic…

Chemical Physics · Physics 2026-02-03 Niels-Ole Frerick , Michael Roemelt , Eric W. Fischer

Polaritons have gained significant attention for the tantalizing possibility of modifying chemical properties and dynamics by coupling molecules to resonant cavity modes to create hybrid light-matter quantum states. Herein, we implement the…

Chemical Physics · Physics 2025-06-24 Scott M. Garner , Xiaosong Li , Sharon Hammes-Schiffer

Polaritons - hybrid light-matter states formed from the strong coupling of a bright molecular transition with a confined photonic mode - may offer new opportunities for optical control of molecular behavior. Vibrational strong coupling…

Chemical Physics · Physics 2025-11-19 Liying Chen , Alexander M. McKillop , Ashley P. Fidler , Marissa L. Weichman

Recent experiments in polariton chemistry have demonstrated that reaction rates can be modified by vibrational strong coupling to an optical cavity mode. Importantly, this modification only occurs when the frequency of the cavity mode is…

Chemical Physics · Physics 2023-05-15 Marit R. Fiechter , Johan E. Runeson , Joseph E. Lawrence , Jeremy O. Richardson

Recent experiments showed that the chemical reaction rate is modified, either increased or decreased, by strongly coupling a nuclear vibration mode to the single mode of an optical cavity. Herein we investigate how the rate of an…

Chemical Physics · Physics 2020-05-04 Nguyen Thanh Phuc , Pham Quang Trung , Akihito Ishizaki

A quantum simulation of vibrational strong coupling (VSC) in the collective regime via thermostatted ring-polymer molecular dynamics (TRPMD) is reported. For a collection of liquid-phase water molecules resonantly coupled to a single…

Chemical Physics · Physics 2022-03-08 Tao E. Li , Abraham Nitzan , Sharon Hammes-Schiffer , Joseph E. Subotnik

Recent experiments have revealed the profound effect of strong light-matter interactions in optical cavities on the electronic ground state of molecular systems. This phenomenon, known as vibrational strong coupling (VSC), can modify…

Quantum Physics · Physics 2023-12-19 Thomas Schnappinger , Markus Kowalewski

Interaction between light and molecular vibrations leads to hybrid light-matter states called vibrational polaritons. Even though many intriguing phenomena have been predicted for single-molecule vibrational strong coupling (VSC), several…

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