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.
manuscript (33 pages) + SI (13 pages) + TOC figure (1 page)
References in corpus (6)
- Quantum Electrodynamical Density-Functional Theory: Bridging Quantum Optics and Electronic-Structure Theory
- Molecular polaritonics: Chemical Dynamics under strong Light-Matter Coupling
- Development of a Practical Multicomponent Density Functional for Electron-Proton Correlation to Produce Accurate Proton Densities
- Quantum-Electrodynamical Time-Dependent Density Functional Theory. I. A Gaussian Atomic Basis Implementation
- Benchmarking Semiclassical and Perturbative Methods for Real-time Simulations of Cavity-Bound Emission and Interference
- Predictive Semiclassical Model for Coherent and Incoherent Emission in the Strong Field Regime: The Mollow Triplet Revisited