Swinging between shine and shadow: Theoretical advances on thermally-activated vibropolaritonic chemistry (a perspective)
arXiv:2212.04017 · doi:10.1063/5.0143253
Abstract
Polariton chemistry has emerged as an appealing branch of synthetic chemistry that promises mode selectivity and a cleaner approach to kinetic control. Of particular interest are the numerous experiments in which reactivity has been modified by virtue of performing the reaction inside infrared optical microcavities in the absence of optical pumping; this effort is known as "vibropolaritonic chemistry." The optimal conditions for these observations are (1) resonance between cavity and reactive modes at normal incidence (), and (2) monotonic increase of the effect with the concentration of emitters in the sample. Importantly, vibropolaritonic chemistry has only been experimentally demonstrated in the so-called "collective" strong coupling regime, where there is a macroscopic number of molecules (rather than a single molecule) coupled to each photon mode of the microcavity. Strikingly, efforts to understand this phenomenon from a conceptual standpoint have encountered several roadblocks and no single, unifying theory has surfaced thus far. This perspective documents the most relevant approaches taken by theorists, laying out the contributions and unresolved challenges from each work. We expect this manuscript to not only serve as a primer for experimentalists and theorists alike, but also inform future endeavors in the quest for the ultimate formalism of vibropolaritonic chemical kinetics.
arXiv comment18 pages, 5 figures
References in corpus (48)
- Cavity quantum electrodynamics for superconducting electrical circuits: an architecture for quantum computation
- Ultrastrong coupling between light and matter
- Ultrastrong coupling regimes of light-matter interaction
- Conductivity in organic semiconductors hybridized with the vacuum field
- Cavity-controlled chemistry in molecular ensembles
- Atoms and Molecules in Cavities: From Weak to Strong Coupling in QED Chemistry
- Coherent coupling of molecular resonators with a micro-cavity mode
- Cavity-induced modifications of molecular structure in the strong coupling regime
- Molecular polaritons for controlling chemistry with quantum optics
- Light-matter interaction in the long-wavelength limit: no ground-state without dipole self-energy
- Resonant catalysis of thermally-activated chemical reactions via vibrational polaritons
- Quantum theory of collective strong coupling of molecular vibrations with a microcavity mode
- Cavity Casimir-Polder forces and their effects in ground state chemical reactivity
- Cavity Born-Oppenheimer Approximation for Correlated Electron-Nuclear-Photon Systems
- Molecular polaritonics: Chemical Dynamics under strong Light-Matter Coupling
- Theoretical Challenges in Polaritonic Chemistry
- Ab-initio non-relativistic quantum electrodynamics: Bridging quantum chemistry and quantum optics from weak to strong coupling
- Shining Light on the Microscopic Resonant Mechanism Responsible for Cavity-Mediated Chemical Reactivity
- Polariton-assisted Singlet Fission in Acene Aggregates
- On the Origin of Ground-State Vacuum-Field Catalysis: Equilibrium Consideration
- Coherent dynamics in cavity femtochemistry: application of the multi-configuration time-dependent Hartree method
- Dark state semilocalization of quantum emitters in a cavity
- Catalysis by Dark States in Vibropolaritonic Chemistry
- A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity
- Resolution of Gauge Ambiguities in Molecular Cavity Quantum Electrodynamics
- Polaritonic normal modes in Transition State Theory
- Electron transfer in confined electromagnetic fields
- Manipulating Optical Nonlinearities of Molecular Polaritons by Delocalization
- Signatures of Vibrational Strong Coupling in Raman Scattering
- Theory of Vibrational Polariton Chemistry in the Collective Coupling Regime
- Two-dimensional Infrared Spectroscopy of vibrational polaritons of molecules in an optical cavity
- Multi-level quantum Rabi model for anharmonic vibrational polaritons
- Resonant Cavity Modification of Ground State Chemical Kinetics
- The Shape of the Electric Dipole Function Determines the Sub-Picosecond Dynamics of Anharmonic Vibrational Polaritons
- Enhanced optical nonlinearities under strong light-matter coupling
- Raman scattering with strongly coupled vibron-polaritons
- Cavity-Altered Thermal Isomerization Rates and Dynamical Resonant Localization in Vibro-Polaritonic Chemistry
- Nonequilibrium effects of cavity leakage and vibrational dissipation in thermally-activated polariton chemistry
- Generalization of the Tavis-Cummings model for multi-level anharmonic systems: insights on the second excitation manifold
- Dynamic of Single Molecules in Collective Light-Matter States from First Principles
- Semiclassical instanton formulation of Marcus-Levich-Jortner theory
- Chemical reactivity under collective vibrational strong coupling
- Generalization of the Tavis-Cummings model for multi-level anharmonic systems
- Dissociation dynamics of a diatomic molecule in an optical cavity
- Vibropolaritonic Reaction Rates in the Collective Strong Coupling Regime: Pollak-Grabert-Hänggi Theory
- Generation of Rabi frequency radiation using exciton-polaritons
- Ultrastrong time-dependent light-matter interactions are gauge-relative
- The gauge-invariant Lagrangian, the Power-Zienau-Woolley picture, and the choices of field momenta in nonrelativistic quantum electrodynamics
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- Cavity-Born-Oppenheimer Hartree-Fock Ansatz: Light-matter Properties of Strongly Coupled Molecular Ensembles
- Unraveling a cavity induced molecular polarization mechanism from collective vibrational strong coupling
- Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong coupling
- Exploring the impact of vibrational cavity coupling strength on ultrafast CN + -CH reaction dynamics
- Vibrational strong coupling in liquid water from cavity molecular dynamics
- When do molecular polaritons behave like optical filters?
- Investigating the Collective Nature of Cavity Modified Chemical Kinetics under Vibrational Strong Coupling
- Dissociation dynamics of a diatomic molecule in an optical cavity
- Ab-Initio Vibro-Polaritonic Spectra in Strongly Coupled Cavity-Molecule Systems
- Vibropolaritonic Reaction Rates in the Collective Strong Coupling Regime: Pollak-Grabert-Hänggi Theory
- Cavity engineering of solid-state materials without external driving
- A versatile platform for gas-phase molecular polaritonics
- Collective Polaritonic Effects on Chemical Dynamics Suppressed by Disorder
- More than just smoke and mirrors: Gas-phase polaritons for optical control of chemistry
- An efficient and flexible approach for computing rovibrational polaritons from first principles
- Extending the Tavis-Cummings model for molecular ensembles -- Exploring the effects of dipole self energies and static dipole moments
- Blackbody radiation and thermal effects on chemical reactions and phase transitions in cavities
- A Cavity-Enhanced Spectroscopist's Lens on Molecular Polaritons
- Open quantum dynamics with variational non-Gaussian states and the truncated Wigner approximation
- On-the-Fly Cavity-Molecular Dynamics of Vibrational Polaritons
- Cavity-Mediated Collective Resonant Suppression of Local Molecular Vibrations
- Polaritonic control of blackbody infrared radiative dissociation