Manipulating azobenzene photoisomerization through strong light-molecule coupling
arXiv:1811.07648 · doi:10.1038/s41467-018-06971-y
Abstract
The formation of hybrid light-molecule states (polaritons) offers a new strategy to manipulate the photochemistry of molecules. To fully exploit its potential, one needs to build a toolbox of polaritonic phenomenologies that supplement those of standard photochemistry. By means of a state-of-the-art computational photochemistry approach extended to the strong-coupling regime, here we disclose various mechanisms peculiar of polaritonic chemistry: coherent population oscillations between polaritons, quenching by trapping in dead-end polaritonic states and the alteration of the photochemical reaction pathway and quantum yields. We focus on azobenzene photoisomerization, that encompasses the essential features of complex photochemical reactions such as the presence of conical intersections and reaction coordinates involving multiple internal modes. In the strong coupling regime, a polaritonic conical intersection arises and we characterize its role in the photochemical process. Our chemically detailed simulations provide a framework to rationalize how the strong coupling impacts the photochemistry of realistic molecules
Published by Springer-Nature publisher group under a CC BY 4.0 license
References in corpus (7)
- Canonical sampling through velocity-rescaling
- Atoms and Molecules in Cavities: From Weak to Strong Coupling in QED Chemistry
- Suppressing photochemical reactions with quantized light fields
- Cavity-induced modifications of molecular structure in the strong coupling regime
- Cavity Born-Oppenheimer Approximation for Correlated Electron-Nuclear-Photon Systems
- Non-adiabatic dynamics of molecules in optical cavities
- Coherent dynamics in cavity femtochemistry: application of the multi-configuration time-dependent Hartree method
Cited by in corpus (39)
- Molecular polaritons for controlling chemistry with quantum optics
- Coupled Cluster Theory for Molecular Polaritons: Changing Ground and Excited States
- Theoretical Challenges in Polaritonic Chemistry
- A perspective on ab initio modeling of polaritonic chemistry: The role of non-equilibrium effects and quantum collectivity
- Molecular orbital theory in cavity QED environments
- Strong coupling with light enhances the photoisomerization quantum yield of azobenzene
- Quantum-Electrodynamical Time-Dependent Density Functional Theory. I. A Gaussian Atomic Basis Implementation
- Abundance of cavity-free polaritonic states in resonant materials and nanostructures
- Equation-of-motion cavity quantum electrodynamics coupled-cluster theory for electron attachment
- Enhanced diastereocontrol via strong light-matter interactions in an optical cavity
- Disorder enhanced vibrational entanglement and dynamics in polaritonic chemistry
- Simulating Photodissociation Reactions in Bad Cavities with the Lindblad Equation
- Nonequilibrium effects of cavity leakage and vibrational dissipation in thermally-activated polariton chemistry
- Dynamic of Single Molecules in Collective Light-Matter States from First Principles
- Non-Adiabatic Molecular Dynamics of Molecules in the Presence of Strong Light-Matter Interactions
- Assessing the Effects of Orbital Relaxation and the Coherent-State Transformation in Quantum Electrodynamics Density Functional and Coupled-Cluster Theories
- Semiclassical Real-Time Nuclear-Electronic Orbital Dynamics for Molecular Polaritons: Unified Theory of Electronic and Vibrational Strong Couplings
- On the characteristic features of ionization in QED environments
- A Shortcut to Self-Consistent Light-Matter Interaction and Realistic Spectra from First-Principles
- Quasi-Diabatic Propagation Scheme for Simulating Polariton Chemistry
- Collective Strong Coupling Modifies Aggregation and Solvation
- Polaritonic Molecular Clock: All-Optical Ultrafast Imaging of Wavepacket Dynamics without Probe Pulses
- Probing Light-Induced Conical Intersections by Monitoring Multidimensional Polaritonic Surfaces
- Nonequilibrium Solvent Polarization Effects in Real-Time Electronic Dynamics of Solute Molecules Subject to Time-Dependent Electric Fields: A New Feature of the Polarizable Continuum Model
- Effective single mode methodology for strongly coupled multimode molecular-plasmon nanosystems
- Efficient parallel strategy for molecular plasmonics -- a numerical tool for integrating Maxwell-Schrodinger equations in three dimensions
- Radiative Emission of Polaritons Controlled by Light-Induced Geometric Phase
- Coupling Polyatomic Molecules to Lossy Nanocavities: Lindblad versus Schrödinger description
- Classical and quantum light-induced non-adiabaticity in molecular systems
- Disordered ensembles of strongly coupled single-molecule plasmonic picocavities as nonlinear optical metamaterials
- Mean-field Mixed Quantum-Classical Approach for Many-Body Quantum Dynamics of Exciton-Polaritons
- Virial relations for electrons coupled to quantum field modes
- Impact of Cavity on Molecular Ionization Spectra
- Impact of dipole self-energy on cavity-induced nonadiabatic dynamics
- Practical guide to the statistical mechanics of molecular polaritons
- Direct readout of excited state lifetimes in chlorin chromophores under electronic strong coupling
- Simulating polaritonic ground states on noisy quantum devices
- Wavefunction Embedding for Molecular Polaritons
- Indirect probing of light-induced nonadiabatic dynamics in lossy nanocavities