Collective conical intersections through light-matter coupling in a cavity

Abstract

The ultrafast non-radiative relaxation of a molecular ensemble coupled to a cavity mode is considered theoretically and by real-time quantum dynamics. For equal coupling strength of single molecules to the cavity mode, the non-radiative relaxation rate from the upper to the lower polariton states is found to strongly depend on the number of coupled molecules. For N>2 molecules, the N-1 dark light-matter states between the two optically active polaritons feature true collective conical intersection crossings, whose location depends on the internal atomic coordinates of each molecule in the ensemble, and which contribute to the ultrafast non-radiative decay from the upper polariton. At least N=3 coupled molecules are necessary for cavity-induced collective conical intersections to exist and, for identical molecules, they constitute a special case of the Jahn-Teller effect.

5 pages, 2 figures. Same conclusions as before, some reformulations after receiving feedback. One figure removed to stay within page limits

References in corpus (4)

• Cavity enhanced transport of excitons
• Multiple Rabi Splittings under Ultra-Strong Vibrational Coupling
• Coherent dynamics in cavity femtochemistry: application of the multi-configuration time-dependent Hartree method
• Organic Polaritons Enable Local Vibrations to Drive Long-Range Energy Transfer

Cited by in corpus (41)

• Molecular polaritons for controlling chemistry with quantum optics
• Cavity Casimir-Polder forces and their effects in ground state chemical reactivity
• Theoretical Challenges in Polaritonic Chemistry
• Catalysis by Dark States in Vibropolaritonic Chemistry
• Polaritonic Coupled-Cluster Theory
• Electron transfer in confined electromagnetic fields
• Ultrafast dynamics in the vicinity of quantum light-induced conical intersections
• Disorder enhanced vibrational entanglement and dynamics in polaritonic chemistry
• Reduced Density-Matrix Approach to Strong Matter-Photon Interaction
• Dynamic of Single Molecules in Collective Light-Matter States from First Principles
• Light-matter hybrid-orbital-based first-principles methods: the influence of the polariton statistics
• Chiral Polaritonics: Analytic Solutions, Intuition and its Use
• Molecular photodissociation enabled by ultrafast plasmon decay
• A quantum optics approach to photoinduced electron transfer in cavities
• Molecule-photon interactions in phononic environments
• Real-Space, Real-Time Approach to Quantum-Electrodynamical Time-Dependent Density Functional Theory
• Quantum Control with Quantum Light of Molecular Nonadiabaticity
• Non-Hermitian molecular dynamics simulations of exciton-polaritons in lossy cavities
• Multidimensional Coherent Spectroscopy of Molecular Polaritons: Langevin Approach
• Nonadiabatic phenomena in molecular vibrational polaritons
• Three-player polaritons: nonadiabatic fingerprints in an entangled atom-molecule-photon system
• Probing Light-Induced Conical Intersections by Monitoring Multidimensional Polaritonic Surfaces
• The role of dephasing for dark state coupling in a molecular Tavis-Cummings model
• Cooperative molecular structure in polaritonic and dark states
• Dissociation slowdown by collective optical response under strong coupling conditions
• Collective Rayleigh Scattering from Molecular Ensembles under Strong Coupling
• Simple but accurate estimation of light-matter coupling strength and optical loss for a molecular emitter coupled with photonic modes
• Coupling Polyatomic Molecules to Lossy Nanocavities: Lindblad versus Schrödinger description
• Classical and quantum light-induced non-adiabaticity in molecular systems
• Ultrafast modulation of vibrational polaritons for controlling the quantum field statistics at mid-infrared frequencies
• Impact of Cavity on Molecular Ionization Spectra
• Cavity Jahn-Teller Polaritons in Molecules
• Impact of dipole self-energy on cavity-induced nonadiabatic dynamics
• Practical guide to the statistical mechanics of molecular polaritons
• Ab initio study on the dynamics and spectroscopy of collective rovibrational polaritons
• Pauli principle in polaritonic chemistry
• Entanglement and correlations in an exactly-solvable model of a Bose-Einstein condensate in a cavity
• Extended Lipkin-Meshkov-Glick Hamiltonian
• Many Electrons and the Photon Field -- The many-body structure of nonrelativistic quantum electrodynamics
• Not dark yet: strong light-matter coupling can accelerate singlet fission dynamics
• Indirect probing of light-induced nonadiabatic dynamics in lossy nanocavities