Molecular orbital theory in cavity QED environments

Abstract

Coupling between molecules and vacuum photon fields inside an optical cavity has proven to be an effective way to engineer molecular properties, in particular reactivity. To ease the rationalization of cavity induced effects we introduce an ab initio method leading to the first fully consistent molecular orbital theory for quantum electrodynamics environments. Our framework is non-perturbative and explains modifications of the electronic structure due to the interaction with the photon field. We show that the newly developed orbital theory can be used to predict cavity induced modifications of molecular reactivity and pinpoint classes of systems with significant cavity effects. We also investigate cavity-induced modifications of molecular reactivity in the vibrational strong coupling regime.

23 pages, 7 figures

References in corpus (12)

• Coherent coupling of molecular resonators with a micro-cavity mode
• Quantum Electrodynamical Density-Functional Theory: Bridging Quantum Optics and Electronic-Structure Theory
• Shining Light on the Microscopic Resonant Mechanism Responsible for Cavity-Mediated Chemical Reactivity
• Intermolecular interactions in optical cavities: an ab initio QED study
• Catalysis by Dark States in Vibropolaritonic Chemistry
• Cavity Quantum-Electrodynamical Chern Insulator: Route Towards Light-Induced Quantized Anomalous Hall Effect in Graphene
• Resolution of Gauge Ambiguities in Molecular Cavity Quantum Electrodynamics
• Cavity-modulated ionization potentials and electron affinities from quantum electrodynamics coupled-cluster theory
• Cavity Quantum Electrodynamics at Arbitrary Light-Matter Coupling Strengths
• Cavity molecular dynamics simulations of vibrational polariton enhanced molecular nonlinear absorption
• Strong coupling between localized surface plasmons and molecules by coupled cluster theory
• Light-matter hybrid-orbital-based first-principles methods: the influence of the polariton statistics

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• 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
• Variational Lang-Firsov approach plus Møller-Plesset perturbation theory with applications to ab initio polariton chemistry
• Real-Space, Real-Time Approach to Quantum-Electrodynamical Time-Dependent Density Functional Theory
• On the characteristic features of ionization in QED environments
• Machine Learning for Polaritonic Chemistry: Accessing chemical kinetics
• Effective single mode methodology for strongly coupled multimode molecular-plasmon nanosystems
• Electronic Born-Oppenheimer Approximation in Nuclear-Electronic Orbital Dynamics
• Selective Excitation of IR-Inactive Modes via Vibrational Polaritons: Insights from Atomistic Simulations
• Photon condensation, Van Vleck paramagnetism, and chiral cavities
• Understanding polaritonic chemistry from ab initio quantum electrodynamics
• Electroluminescence rectification and high harmonic generation in molecular junctions
• Microscopic theory of Raman scattering for the rotational organic cation in metal halide perovskites
• Cavity Born-Oppenheimer Coupled Cluster Theory: Towards Electron Correlation in the Vibrational Strong Light-Matter Coupling Regime
• Deep quantum Monte Carlo approach for polaritonic chemistry
• Ab Initio Polaritonic Chemistry on Diverse Quantum Computing Platforms: Qubit, Qudit, and Hybrid Qubit-Qumode Architectures
• Cavity-Modified Zeeman Effect via Spin-Polariton Formation
• Polariton-induced Purcell effects via a reduced semiclassical electrodynamics approach
• Scalable Quantum Monte Carlo Method for Polariton Chemistry via Mixed Block Sparsity and Tensor Hypercontraction Method