Disorder enhanced vibrational entanglement and dynamics in polaritonic chemistry

Abstract

Collectively coupling molecular ensembles to a cavity has been demonstrated to modify chemical reactions akin to catalysis. Theoretically understanding this experimental finding remains to be an important challenge. In particular the role of quantum effects in such setups is an open question of fundamental and practical interest. Theoretical descriptions often neglect quantum entanglement between nuclear and electro-photonic degrees of freedom, e.g.~by computing Ehrenfest dynamics. Here we discover that disorder can strongly enhance the build-up of this entanglement on short timescales after incoherent photo-excitation. We find that this can have direct consequences for reaction coordinate dynamics. We analyze this phenomenon in a disordered Holstein-Tavis-Cummings model, a minimal toy model that includes all fundamental degrees of freedom. Using a numerical technique based on matrix product states we simulate the exact quantum dynamics of more than 100 molecules. Our results highlight the importance of beyond Born-Oppenheimer theories in polaritonic chemistry.

8 pages, 5 figures (+ 8 pages Appendix)

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• Machine Learning for Polaritonic Chemistry: Accessing chemical kinetics
• Controlling the Manifold of Polariton States Through Molecular Disorder
• Collective Strong Coupling Modifies Aggregation and Solvation
• Collective Polaritonic Effects on Chemical Dynamics Suppressed by Disorder
• The role of dephasing for dark state coupling in a molecular Tavis-Cummings model
• Cavity-Catalyzed Hydrogen Transfer Dynamics in an Entangled Molecular Ensemble under Vibrational Strong Coupling
• Photochemical Initiation of Polariton Propagation
• Coupling Polyatomic Molecules to Lossy Nanocavities: Lindblad versus Schrödinger description
• Impact of Cavity on Molecular Ionization Spectra
• Understanding polaritonic chemistry from ab initio quantum electrodynamics
• Multiple Interacting Photonic Modes in Strongly Coupled Organic Microcavities
• The role of dark polariton states for electronic strong coupling in molecules
• Open quantum dynamics with variational non-Gaussian states and the truncated Wigner approximation
• The iSWAP gate with polar molecules: Robustness criteria for entangling operations
• Disorder-Induced Spectral Splitting versus Rabi Splitting under Strong Light-Matter Coupling
• Ab Initio Polaritonic Chemistry on Diverse Quantum Computing Platforms: Qubit, Qudit, and Hybrid Qubit-Qumode Architectures
• Theory of dynamical superradiance in organic materials