Theoretical Challenges in Polaritonic Chemistry

@article{Fregoni2022TheoreticalCI,
  title={Theoretical Challenges in Polaritonic Chemistry},
  author={Jacopo Fregoni and Francisco J. Garc{\'i}a-Vidal and Johannes Feist},
  journal={ACS Photonics},
  year={2022},
  volume={9},
  pages={1096 - 1107}
}
Polaritonic chemistry exploits strong light–matter coupling between molecules and confined electromagnetic field modes to enable new chemical reactivities. In systems displaying this functionality, the choice of the cavity determines both the confinement of the electromagnetic field and the number of molecules that are involved in the process. While in wavelength-scale optical cavities the light–matter interaction is ruled by collective effects, plasmonic subwavelength nanocavities allow even… 

Figures from this paper

A Theoretical Perspective on Molecular Polaritonics

In the past decade, much theoretical research has focused on studying the strong coupling between organic molecules (or quantum emitters, in general) and light modes. The description and prediction

Wavefunction embedding for molecular polaritons.

Polaritonic chemistry relies on the strong light-matter interaction phenomena for altering the chemical reaction rates inside optical cavities. To explain and understand these processes, the

Ultrafast collapse of molecular polaritons in photoswitch-nanoantennas at room temperature

Molecular polaritons are hybrid light-matter states that emerge when a molecular transition strongly interacts with photons in a resonator. At optical frequencies, this interaction unlocks a way to

Dynamical mean-field study of a photon-mediated ferroelectric phase transition

The interplay of light and matter gives rise to intriguing cooperative effects in quantum many-body systems. This is even true in thermal equilibrium, where the electromagnetic field can hybridize with

Certifying multi-mode light-matter interaction in lossy resonators

Quantum models based on few-mode Master equations have been a central tool in the study of resonator quantum electrodynamics, extending the seminal single-mode Jaynes-Cummings model to include loss

Influence of Vibrational Strong Coupling on an Ordered Liquid Crystal.

Vibrational strong coupling and the formation of vibrational polaritons are a result of strong light-matter interaction between a cavity photon and a molecular vibrational mode. The Rabi splitting

Collective dynamics Using Truncated Equations (CUT-E): simulating the collective strong coupling regime with few-molecule models

The study of molecular polaritons beyond simple quantum emitter ensemble models (e.g., Tavis-Cummings) is challenging due to the large dimensionality of these systems (the number of molecular

Something from nothing: linking molecules with virtual light

A new research field is emerging in which ensembles of molecules are collectively hybridised with light in a process known as strong coupling. This hybridisation leads to the formation of new states

Influence of a gold nano-bumps surface lattice array on the propagation length of strongly coupled Tamm and surface plasmon polaritons

Controlling and increasing the propagation length between Tamm and surface plasmons under a strong coupling regime using surface lattice arrays leads to better coherence properties of hybrid

Permutational symmetry for identical multilevel systems: A second-quantized approach

We develop a framework that provides a straightforward approach to fully exploit the permutational symmetry of identical multi-level systems. By taking into account the permutational symmetry, we

References

SHOWING 1-10 OF 154 REFERENCES

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.

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.

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.

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.

Strong Coupling between Localized Surface Plasmons and Molecules by Coupled Cluster Theory

This work presents a nonperturbative method to simulate the emerging properties of polaritons, which combines a high-level quantum chemical description of the molecule with a quantized descriptions of the localized surface plasmons in the nanocavity.

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.

Theory for polariton-assisted remote energy transfer

Strong-coupling between light and matter produces hybridized states (polaritons) whose delocalization and electromagnetic character allow for novel modifications in spectroscopy and chemical

Cavity Femtochemistry: Manipulating Nonadiabatic Dynamics at Avoided Crossings.

Numerical results show how the branching ratio between the covalent and ionic dissociation channels can be strongly manipulated by the optical cavity, avoiding the limitations set by the rotating wave approximation when the field is expanded in Fock space.

Polaritonic Chemistry with Organic Molecules

We present an overview of the general concepts of polaritonic chemistry with organic molecules, i.e., the manipulation of chemical structure that can be achieved through strong coupling between

Controlling the Photostability of Pyrrole with Optical Nanocavities

The results show how the optical cavities assist in controlling the photostability of pyrrole and influence the reaction mechanism by providing alternative dissociation pathways, and demonstrate the importance of the vibrational cavity couplings and dipole-self interaction terms in describing the cavity-modified non-adiabatic dynamics.
...