Exact Potential Energy Surface for Molecules in Cavities

Abstract

We find and analyze the exact time-dependent potential energy surface driving the proton motion for a model of cavity-induced suppression of proton-coupled electron-transfer. We show how, in contrast to the polaritonic surfaces, its features directly correlate to the proton dynamics and discuss cavity-modifications of its structure responsible for the suppression. The results highlight the interplay between non-adiabatic effects from coupling to photons and coupling to electrons, and suggest caution is needed when applying traditional dynamics methods based on polaritonic surfaces.

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Cited by in corpus (21)

• Molecular polaritonics: Chemical Dynamics under strong Light-Matter Coupling
• Theoretical Challenges in Polaritonic Chemistry
• Real-time solutions of coupled Ehrenfest-Maxwell-Pauli-Kohn-Sham equations: fundamentals, implementation, and nano-optical applications
• Ultrafast dynamics with the exact factorization
• Cavity-Altered Thermal Isomerization Rates and Dynamical Resonant Localization in Vibro-Polaritonic Chemistry
• Real-Space, Real-Time Approach to Quantum-Electrodynamical Time-Dependent Density Functional Theory
• Quasi-Diabatic Propagation Scheme for Simulating Polariton Chemistry
• Case Studies of the Time-Dependent Potential Energy Surface for Dynamics in Cavities
• Collective response in light-matter interactions: The interplay between strong coupling and local dynamics
• Multidimensional Coherent Spectroscopy of Molecular Polaritons: Langevin Approach
• Quantum-classical nonadiabatic dynamics of Floquet driven systems
• Collective Polaritonic Effects on Chemical Dynamics Suppressed by Disorder
• Analysis of the Classical Trajectory Treatment of Photon Dynamics for Polaritonic Phenomena
• Fock space embedding theory for strongly correlated topological phases
• Efficient parallel strategy for molecular plasmonics -- a numerical tool for integrating Maxwell-Schrodinger equations in three dimensions
• Stochastic Variational Approach to Small Atoms and Molecules Coupled to Quantum Field Modes
• Generation of macroscopic entangled cat states in a molecular cavity-QED system
• Understanding polaritonic chemistry from ab initio quantum electrodynamics
• Wavefunction Embedding for Molecular Polaritons
• Energy spectrum and structure of one-dimensional few-electron Wigner crystals with and without coupling to light in cavity
• Two electrons in harmonic confinement coupled to light in a cavity