Molecular Polaritonics: Chemical Dynamics Under Strong Light-Matter Coupling.

  title={Molecular Polaritonics: Chemical Dynamics Under Strong Light-Matter Coupling.},
  author={Tao E. Li and Bingyu Cui and Joseph E Subotnik and Abraham Nitzan},
  journal={Annual review of physical chemistry},
Chemical manifestations of strong light-matter coupling have recently been a subject of intense experimental and theoretical studies. Here we review the present status of this field. Section 1 is an introduction to molecular polaritonics and to collective response aspects of light-matter interactions. Section 2 provides an overview of the key experimental observations of these effects, while Section 3 describes our current theoretical understanding of the effect of strong light-matter coupling… 

Figures from this paper

Multimode polariton effects on molecular energy transport and spectral fluctuations

  • R. Ribeiro
  • Physics, Chemistry
    Communications Chemistry
  • 2022
Despite the potential paradigm breaking capability of microcavities to control chemical processes, the extent to which photonic devices change properties of molecular materials is still unclear, in

Understanding polaritonic chemistry from ab initio quantum electrodynamics

In this review we present the theoretical foundations and first principles frameworks to describe quantum matter within quantum electrodynamics (QED) in the low-energy regime, with a specific focus

Semiclassical Real-Time Nuclear-Electronic Orbital Dynamics for Molecular Polaritons: Unified Theory of Electronic and Vibrational Strong Couplings.

Molecular polaritons have become an emerging platform for remotely controlling molecular properties through strong light-matter interactions. Herein, a semiclassical approach is developed for

Multidimensional Quantum Dynamical Simulation of Infrared Spectra under Polaritonic Vibrational Strong Coupling.

Recent experimental and theoretical studies demonstrate that the chemical reactivity of molecules can be modified inside an optical cavity. Here, we provide a theoretical framework for conducting

Dissociation slowdown by collective optical response under strong coupling conditions

We consider an ensemble of diatomic molecules resonantly coupled to a resonant optical cavity under strong coupling conditions at normal incidence. Photodissociation dynamics is examined via direct

Vibrational Polaritons in Disordered Molecular Ensembles

Disorder is an intrinsic attribute of any realistic molecular system. It is known to lead to localization, which hampers efficient transport. It was recently proposed that in molecular ensembles

Cavity-Free Quantum-Electrodynamic Electron Transfer Reactions.

Richard Feynman stated that "The theory behind chemistry is quantum electrodynamics". However, harnessing quantum-electrodynamic (QED) effects to modify chemical reactions is a grand challenge and

Effects of Electron-Vibration Interaction in Polariton Luminescence: Non-Markovian Fano Resonances and Hot Luminescence.

We have developed a non-Markovian theory of the polariton luminescence taking the molecular vibrations into account. The calculations were performed in the polariton basis. We have shown that the

Quantum Simulations of Vibrational Strong Coupling via Path Integrals.

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

Strong Coupling in Infrared Plasmonic Cavities.

Controlling molecular spectroscopy and even chemical behavior in a cavity environment is a subject of intense experimental and theoretical interest. In Fabry-Pérot cavities, strong (radiation-matter)



Molecular polaritons for controlling chemistry with quantum optics.

The basic physical principles and consequences of strong light-matter coupling common to molecular ensembles embedded in UV-visible or infrared cavities are described and the competition between the collective cooperative dipolar response of a molecular ensemble and local dynamical processes that molecules typically undergo are discussed.

Polaritonic Chemistry: Collective Strong Coupling Implies Strong Local Modification of Chemical Properties.

These findings suggest that recently developed ab initio methods for strong light-matter coupling are suitable to access these local polaritonic effects and provide a detailed understanding of photon-modified chemistry.

Multi-scale dynamics simulations of molecular polaritons: The effect of multiple cavity modes on polariton relaxation.

The results of the simulations suggest that after resonant excitation into the upper polariton at a fixed wave vector, or incidence angle, the coupled cavity-molecule system rapidly decays into dark states that lack dispersion, and it is anticipated that the more realistic cavity description in this approach will help to better understand and predict how cavities can modify molecular properties.

Atom Assisted Photochemistry in Optical Cavities

This work presents a model system that simplifies the problem by mixing two-level Mg atoms with a single MgH+ molecule and investigates its collective dynamics, and presents quantum dynamics simulations of the coupled vibronic–photonic system for a variable size of the atomic ensemble.

Polaritonic normal modes in transition state theory.

It is concluded that further studies are necessary to track the origin of the experimentally observed kinetics, and a normal mode analysis of the transition state and reactant configurations for an ensemble of an arbitrary number of molecules in a cavity produces simple analytical expressions that produce similar conclusions as Feist.

Multiscale Molecular Dynamics Simulations of Polaritonic Chemistry.

A multiscale quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulation model for photoactive molecules that are strongly coupled to confined light in optical cavities or surface plasmons is presented and it is anticipated that this method will lead to a better understanding of the effects of strong coupling on chemical reactivity.

Tracking Polariton Relaxation with Multiscale Molecular Dynamics Simulations

Atomic molecular dynamics simulations of room-temperature ensembles of rhodamine chromophores strongly coupled to a single confined light mode with a 15 fs lifetime suggest that polaritonic chemistry relying on modified dynamics taking place within the lower polariton manifold requires cavities with sufficiently long lifetimes and, at the same time, strong light–matter coupling strengths to prevent the back-transfer of excitation into the dark states.

Ab initio polaritonic potential-energy surfaces for excited-state nanophotonics and polaritonic chemistry.

A first principles framework to calculate polaritonic excited-state potential-energy surfaces, transition dipole moments, and transition densities for strongly coupled light-matter systems and shows how strong coupling can be exploited to alter photochemical reaction pathways by influencing avoided crossings with tuning of the cavity frequency and coupling strength.

Cavity-Correlated Electron-Nuclear Dynamics from First Principles.

This work introduces a general time-dependent density-functional theory to study correlated electron, nuclear, and photon interactions on the same quantized footing and complements the theoretical formulation with the first ab initio calculation of a correlated electron-nuclear-photon system.

Recent Progress in Vibropolaritonic Chemistry.

This minireview highlights experimental works on vibrational polaritonic chemistry that have appeared most recently, focusing on the chemistry of the rate-limiting steps to provide mechanistic insight and hopes this review will encourage synthetic chemists to enter the field.