Collective Polaritonic Effects on Chemical Dynamics Suppressed by Disorder

Abstract

We present a powerful formalism, disordered collective dynamics using truncated equations (d-CUT-E), to simulate the ultrafast quantum dynamics of molecular polaritons in the collective strong coupling regime, where a disordered ensemble of $N\gg 10^6$ molecules couples to a cavity mode. Notably, we can capture this dynamics with a cavity hosting a single \textit{effective} molecule with $\sim N_{bins}$ electronic states, where $N_{bins}\ll N$ is the number of bins discretizing the disorder distribution. Using d-CUT-E we conclude that strong coupling, as evaluated from linear optical spectra, can be a poor proxy for polariton chemistry. For highly disordered ensembles, total reaction yield upon broadband excitation is identical to that outside of the cavity, while narrowband excitation produces distinct reaction yields solely due to differences in the initial states prepared prior to the reaction.

16 pages, 12 figures

References in corpus (23)

• Multilayer multi-configuration time-dependent Hartree method: implementation and applications to a Henon-Heiles Hamiltonian and to pyrazine
• Ultrafast imaging of polariton propagation and interactions
• Tuning the coherent propagation of organic exciton-polaritons through dark state delocalization
• Swinging between shine and shadow: Theoretical advances on thermally-activated vibropolaritonic chemistry (a perspective)
• Polariton Localization and Dispersion Properties of Disordered Quantum Emitters in Multimode Microcavities
• Unusual Dynamical Properties of Disordered Polaritons in Micocavities
• A theoretical perspective on molecular polaritonics
• Disorder enhanced vibrational entanglement and dynamics in polaritonic chemistry
• Non-polaritonic effects in cavity-modified photochemistry
• Microscopic Theory of Multimode Polariton Dispersion in Multilayered Materials
• Effects of disorder on polaritonic and dark states in a cavity using the disordered Tavis-Cummings model
• Femtosecond Photophysics of Molecular Polaritons
• QM/MM Modeling of Vibrational Polariton Induced Energy Transfer and Chemical Dynamics
• Disorder-enhanced transport in a chain of lossy dipoles strongly coupled to cavity photons
• Vibrational polariton transport in disordered media
• Dissociation dynamics of a diatomic molecule in an optical cavity
• Interplay Between Disorder and Collective Coherent Response: Superradiance and Spectral Motional Narrowing in the Time Domain
• Collective response in light-matter interactions: The interplay between strong coupling and local dynamics
• Ultrafast collapse of molecular polaritons in photoswitch-nanoantennas at room temperature
• Dissipation-driven formation of entangled dark states in strongly-coupled inhomogeneous many-qubit systems in solid-state nanocavities
• Dissociation slowdown by collective optical response under strong coupling conditions
• First principles modeling of exciton-polaritons in polydiacetylene chains
• Efficient linear scaling mapping for permutation symmetric Fock spaces

Cited by in corpus (1)

• When do molecular polaritons behave like optical filters?