Semiclassical Real-Time Nuclear-Electronic Orbital Dynamics for Molecular Polaritons: Unified Theory of Electronic and Vibrational Strong Couplings
arXiv:2203.04952 · doi:10.1021/acs.jctc.2c00096
Abstract
Molecular polaritons have become an emerging platform for remotely controlling molecular properties through strong light-matter interactions. Herein, a semiclassical approach is developed for describing molecular polaritons by self-consistently propagating the real-time dynamics of classical cavity modes and a quantum molecular subsystem described by the nuclear-electronic orbital (NEO) method, where electrons and specified nuclei are treated quantum mechanically on the same level. This semiclassical real-time NEO approach provides a unified description of electronic and vibrational strong couplings and describes the impact of the cavity on coupled nuclear-electronic dynamics while including nuclear quantum effects. For a single o-hydroxybenzaldehyde molecule under electronic strong coupling, this approach shows that the cavity suppression of excited state intramolecular proton transfer is influenced not only by the polaritonic potential energy surface but also by the timescale of the chemical reaction. This work provides the foundation for exploring collective strong coupling in nuclear-electronic quantum dynamical systems within optical cavities.
arXiv commentmanuscript (33 pages) + SI (13 pages) + TOC figure (1 page)
References in corpus (27)
- Ultrastrong coupling between light and matter
- Vacuum Rabi splitting in a plasmonic cavity at the single quantum emitter limit
- Conductivity in organic semiconductors hybridized with the vacuum field
- Atoms and Molecules in Cavities: From Weak to Strong Coupling in QED Chemistry
- Octopus, a computational framework for exploring light-driven phenomena and quantum dynamics in extended and finite systems
- Suppressing photochemical reactions with quantized light fields
- Quantum Electrodynamical Density-Functional Theory: Bridging Quantum Optics and Electronic-Structure Theory
- Molecular polaritons for controlling chemistry with quantum optics
- Resolution of Gauge Ambiguities in Ultrastrong-Coupling Cavity QED
- Coupled Cluster Theory for Molecular Polaritons: Changing Ground and Excited States
- Molecular polaritonics: Chemical Dynamics under strong Light-Matter Coupling
- Manipulating azobenzene photoisomerization through strong light-molecule coupling
- Cavity molecular dynamics simulations of liquid water under vibrational ultrastrong coupling
- Development of a Practical Multicomponent Density Functional for Electron-Proton Correlation to Produce Accurate Proton Densities
- Cavity correlated electron-nuclear dynamics from first principles
- On the Origin of Ground-State Vacuum-Field Catalysis: Equilibrium Consideration
- Macroscopic QED for quantum nanophotonics: Emitter-centered modes as a minimal basis for multi-emitter problems
- Topical Review: optics of exciton-plasmon nanomaterials
- Collective vibrational strong coupling effects on molecular vibrational relaxation and energy transfer: Numerical insights via cavity molecular dynamics simulations
- Quantum-Electrodynamical Time-Dependent Density Functional Theory. I. A Gaussian Atomic Basis Implementation
- Time-dependent density functional theory for interaction of ultrashort light pulse with thin materials
- Benchmarking Semiclassical and Perturbative Methods for Real-time Simulations of Cavity-Bound Emission and Interference
- The Shape of the Electric Dipole Function Determines the Sub-Picosecond Dynamics of Anharmonic Vibrational Polaritons
- Quasiclassical Modeling of Cavity Quantum Electrodynamics
- Analysis of the Classical Trajectory Treatment of Photon Dynamics for Polaritonic Phenomena
- Predictive Semiclassical Model for Coherent and Incoherent Emission in the Strong Field Regime: The Mollow Triplet Revisited
- A Necessary Trade-off for Semiclassical Electrodynamics: Accurate Short-Range Coulomb Interactions versus the Enforcement of Causality?
Cited by in corpus (6)
- Cavity-Born-Oppenheimer Hartree-Fock Ansatz: Light-matter Properties of Strongly Coupled Molecular Ensembles
- Chiral Polaritonics: Analytic Solutions, Intuition and its Use
- Electronic Born-Oppenheimer Approximation in Nuclear-Electronic Orbital Dynamics
- Reaching precise proton affinities in non-Born-Oppenheimer calculations
- Mechanistic principles of exciton-polariton relaxation
- Extended Lagrangian molecular dynamics on vibronic surfaces in the nuclear-electronic orbital framework