Cavity Casimir-Polder forces and their effects in ground state chemical reactivity

Abstract

Here we present a fundamental study on how the ground-state chemical reactivity of a molecule can be modified in a QED scenario, i.e., when it is placed inside a cavity and there is strong coupling between the cavity field and vibrational modes within the molecule. We work with a model system for the molecule (Shin-Metiu model) in which nuclear, electronic and photonic degrees of freedom are treated on the same footing. This simplified model allows the comparison of exact quantum reaction rate calculations with predictions emerging from transition state theory based on the cavity Born-Oppenheimer approach. We demonstrate that QED effects are indeed able to significantly modify activation barriers in chemical reactions and, as a consequence, reaction rates. The critical physical parameter controlling this effect is the permanent dipole of the molecule and how this magnitude changes along the reaction coordinate. We show that the effective coupling can lead to significant single-molecule energy shifts in an experimentally available nanoparticle-on-mirror cavity. We then apply the validated theory to a realistic case (internal rotation in the 1,2-dichloroethane molecule), showing how reactions can be inhibited or catalyzed depending on the profile of the molecular dipole. Furthermore, we discuss the absence of resonance effects in this process, which can be understood through its connection to Casimir-Polder forces. Finally, we treat the case of many-molecule strong coupling, and find collective modifications of reaction rates if the molecular permanent dipole moments are oriented with respected to the cavity field. This demonstrates that collective coupling can also provide a mechanism for modifying ground-state chemical reactivity of an ensemble of molecules coupled to a cavity mode.

arXiv commentrevised version with new title; 22 pages, 9 figures

References in corpus (49)

• Beyond the Jaynes-Cummings model: circuit QED in the ultrastrong coupling regime
• Superconducting qubit-oscillator circuit beyond the ultrastrong-coupling regime
• 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
• Realizing strong light-matter interactions between single nanoparticle plasmons and molecular excitons at ambient conditions
• Coherent coupling of molecular resonators with a micro-cavity mode
• Ultrastrong coupling of a single artificial atom to an electromagnetic continuum in the nonperturbative regime
• Extraordinary exciton conductance induced by strong coupling
• Three-dimensional quantization of the electromagnetic field in dispersive and absorbing inhomogeneous dielectrics
• Boron nitride nanoresonators for phonon-enhanced molecular vibrational spectroscopy at the strong coupling limit
• Suppressing photochemical reactions with quantized light fields
• Cavity-induced modifications of molecular structure in the strong coupling regime
• On the use of Purcell factors for plasmon antennas
• Light-matter interaction in the long-wavelength limit: no ground-state without dipole self-energy
• Effective mode volumes and Purcell factors for leaky optical cavities
• Cavity Born-Oppenheimer Approximation for Correlated Electron-Nuclear-Photon Systems
• Time-dependent density functional theory for many-electron systems interacting with cavity photons
• Ab-initio non-relativistic quantum electrodynamics: Bridging quantum chemistry and quantum optics from weak to strong coupling
• Breakdown of gauge invariance in ultrastrong-coupling cavity QED
• Many-molecule reaction triggered by a single photon in polaritonic chemistry
• Spontaneous Emission Spectra and Quantum Light-Matter Interactions from a Strongly-Coupled Quantum Dot Metal-Nanoparticle System
• Mapping nanoscale hotspots with single-molecule emitters assembled into plasmonic nanocavities using DNA origami
• Ab-initio nanoplasmonics: The impact of atomic structure
• Polariton-assisted Singlet Fission in Acene Aggregates
• Kohn-Sham Approach to Quantum Electrodynamical Density Functional Theory: Exact Time-Dependent Effective Potentials in Real Space
• Cavity quantum electrodynamics in the non-perturbative regime
• Non-adiabatic dynamics of molecules in optical cavities
• Thermal Casimir vs Casimir-Polder forces: Equilibrium and non-equilibrium forces
• Can ultrastrong coupling change ground state chemical reactions?
• Elimination of the A-square problem from cavity QED
• Excitonic spectral features in strongly-coupled organic polaritons
• Exact states and spectra of vibrationally dressed polaritons
• Collective conical intersections through light-matter coupling in a cavity
• Coherent dynamics in cavity femtochemistry: application of the multi-configuration time-dependent Hartree method
• Transformation Optics Approach to Plasmon-Exciton Strong Coupling in Nanocavities
• Perspective: Quantum Hamiltonians for Optical Interactions
• Harvesting Excitons Through Plasmonic Strong Coupling
• Gauge ambiguities imply Jaynes-Cummings physics remains valid in ultrastrong coupling QED
• Signatures of Vibrational Strong Coupling in Raman Scattering
• Organic Polaritons Enable Local Vibrations to Drive Long-Range Energy Transfer
• Reversible dynamics of single quantum emitters near metal-dielectric interfaces
• Resolution of superluminal signalling in non-perturbative cavity quantum electrodynamics
• Theoretical Investigation of Phonon Polaritons in SiC Micropillar Resonators
• Temperature-invariant Casimir-Polder forces despite large thermal photon numbers
• Collective effects in Casimir-Polder forces
• Collective optomechanical effects in cavity quantum electrodynamics
• Generation of Rabi frequency radiation using exciton-polaritons
• Orientational alignment in Cavity Quantum Electrodynamics

Cited by in corpus (84)

• Octopus, a computational framework for exploring light-driven phenomena and quantum dynamics in extended and finite systems
• Molecular polaritons for controlling chemistry with quantum optics
• Resonant catalysis of thermally-activated chemical reactions via vibrational polaritons
• Coupled Cluster Theory for Molecular Polaritons: Changing Ground and Excited States
• Molecular polaritonics: Chemical Dynamics under strong Light-Matter Coupling
• Theoretical Challenges in Polaritonic Chemistry
• Cavity molecular dynamics simulations of liquid water under vibrational ultrastrong coupling
• Intermolecular interactions in optical cavities: an ab initio QED study
• On the Origin of Ground-State Vacuum-Field Catalysis: Equilibrium Consideration
• 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
• Macroscopic QED for quantum nanophotonics: Emitter-centered modes as a minimal basis for multi-emitter problems
• Polaritonic normal modes in Transition State Theory
• Swinging between shine and shadow: Theoretical advances on thermally-activated vibropolaritonic chemistry (a perspective)
• Molecular orbital theory in cavity QED environments
• Theory of Vibrational Polariton Chemistry in the Collective Coupling Regime
• The Free Electron Gas in Cavity Quantum Electrodynamics
• Quantum-Electrodynamical Time-Dependent Density Functional Theory. I. A Gaussian Atomic Basis Implementation
• Abundance of cavity-free polaritonic states in resonant materials and nanostructures
• Cavity molecular dynamics simulations of vibrational polariton enhanced molecular nonlinear absorption
• Resonant Cavity Modification of Ground State Chemical Kinetics
• Weak-to-Strong Light-Matter Coupling and Dissipative Dynamics from First Principles
• Equation-of-motion cavity quantum electrodynamics coupled-cluster theory for electron attachment
• Enhanced diastereocontrol via strong light-matter interactions in an optical cavity
• The Shape of the Electric Dipole Function Determines the Sub-Picosecond Dynamics of Anharmonic Vibrational Polaritons
• Enhancing vibrational light-matter coupling strength beyond the molecular concentration limit using plasmonic arrays
• Strong coupling in chiral cavities: nonperturbative framework for enantiomer discrimination
• Driving chemical reactions with polariton condensates
• Polariton relaxation under vibrational strong coupling: Comparing cavity molecular dynamics simulations against Fermi's golden rule rate
• Quasiclassical Modeling of Cavity Quantum Electrodynamics
• Cavity-Altered Thermal Isomerization Rates and Dynamical Resonant Localization in Vibro-Polaritonic Chemistry
• Reduced Density-Matrix Approach to Strong Matter-Photon Interaction
• Nonequilibrium effects of cavity leakage and vibrational dissipation in thermally-activated polariton chemistry
• Energy-efficient pathway for selectively exciting solute molecules to high vibrational states via solvent vibration-polariton pumping
• Effects of disorder on polaritonic and dark states in a cavity using the disordered Tavis-Cummings model
• Light-matter hybrid-orbital-based first-principles methods: the influence of the polariton statistics
• Beyond Cavity Born-Oppenheimer: On Non-Adiabatic Coupling and Effective Ground State Hamiltonians in Vibro-Polaritonic Chemistry
• QM/MM Modeling of Vibrational Polariton Induced Energy Transfer and Chemical Dynamics
• Molecular photodissociation enabled by ultrafast plasmon decay
• The Vacua of Dipolar Cavity Quantum Electrodynamics
• Real-Space, Real-Time Approach to Quantum-Electrodynamical Time-Dependent Density Functional Theory
• Chemical reactivity under collective vibrational strong coupling
• On the characteristic features of ionization in QED environments
• Investigating the Collective Nature of Cavity Modified Chemical Kinetics under Vibrational Strong Coupling
• Machine Learning for Polaritonic Chemistry: Accessing chemical kinetics
• Reduced-density-matrix-based ab initio cavity quantum electrodynamics
• Dissociation dynamics of a diatomic molecule in an optical cavity
• Engineering flat bands in twisted-bilayer graphene away from the magic angle with chiral optical cavities
• Vibropolaritonic Reaction Rates in the Collective Strong Coupling Regime: Pollak-Grabert-Hänggi Theory
• Cavity engineered phonon-mediated superconductivity in MgB${}_2$ from first principles quantum electrodynamics
• Dispersion Interaction between Two Hydrogen Atoms in a Static Electric Field
• Nonperturbative cavity quantum electrodynamics: is the Jaynes-Cummings model still relevant?
• Vacuum-Induced Symmetry Breaking of Chiral Enantiomer Formation in Chemical Reactions
• An efficient and flexible approach for computing rovibrational polaritons from first principles
• A quantum chemistry approach to linear vibro-polaritonic IR spectra with perturbative electron-photon correlation
• Electronic Born-Oppenheimer Approximation in Nuclear-Electronic Orbital Dynamics
• Superreaction: the collective enhancement of a reaction rate by molecular polaritons in the presence of energy fluctuations
• Coupling Polyatomic Molecules to Lossy Nanocavities: Lindblad versus Schrödinger description
• Relaxation breakdown and resonant tunneling in ultrastrong-coupling cavity QED
• Exact Results for the Tavis-Cummings and H$\ddot{\mathbf{u}}$ckel Hamiltonians with Diagonal Disorder
• Selective Excitation of IR-Inactive Modes via Vibrational Polaritons: Insights from Atomistic Simulations
• Chiral cavity induced spin selectivity
• Virial relations for electrons coupled to quantum field modes
• Bose enhancement of excitation-energy transfer with molecular-exciton-polariton condensates
• Floquet engineering of molecular dynamics via infrared coupling
• Impact of Cavity on Molecular Ionization Spectra
• Description of ultrastrong light-matter interaction through coupled harmonic oscillator models and their connection with cavity-QED Hamiltonians
• Cavity-modified electronic interactions in molecular ensembles under vibrational strong coupling: Combined insights from cavity Born-Oppenheimer perturbation and ab initio wave function theories
• Coupling, lifetimes and "strong coupling" maps for single molecules at plasmonic interfaces
• Impact of dipole self-energy on cavity-induced nonadiabatic dynamics
• Polaritonic control of blackbody infrared radiative dissociation
• Angular Momentum-Dependent Spectral Shift in Chiral Vacuum Cavities
• Deep quantum Monte Carlo approach for polaritonic chemistry
• Cavity-Born Oppenheimer Approximation for Molecules and Materials via Electric Field Response
• Casimir-Lifshitz Theory for Cavity Modification of Ground-State Energy
• Polariton-induced Purcell effects via a reduced semiclassical electrodynamics approach
• Many Electrons and the Photon Field -- The many-body structure of nonrelativistic quantum electrodynamics
• Indirect probing of light-induced nonadiabatic dynamics in lossy nanocavities
• Wavefunction Embedding for Molecular Polaritons
• Cavity-induced bifurcation in classical rate theory
• Collective Effects of Organic Molecules based on Holstein-Tavis-Cummings Model
• Strong light-matter interaction effects on molecular ensembles
• Controlling the nonadiabatic electron-transfer reaction rate through molecular-vibration polaritons in the ultrastrong coupling regime
• Quantum Effects in Chemical Reactions under Polaritonic Vibrational Strong Coupling