Disorder Enhanced Vibrational Entanglement and Dynamics in Polaritonic Chemistry

Collectively coupling molecular ensembles to a cavity has been demonstrated to modify chemical reactions akin to catalysis. Theoretically understanding this experimental finding remains an important challenge, in particular the role of quantum effects. Common theoretical descriptions often neglect quantum entanglement between nuclear and electro-photonic degrees of freedom, for example via Ehrenfest dynamics. Here, we discover that disorder can strongly enhance the build-up of this entanglement on short timescales after incoherent photo-excitation, with direct consequences for nuclear coordinate dynamics. We analyze this phenomenon in a disordered Holstein-Tavis-Cummings model, a minimal model that includes all fundamental degrees of freedom. Using a matrix product state-based numerical technique we simulate the exact quantum dynamics of more than 100 molecules. Our results highlight the importance of beyond Born-Oppenheimer theories in polaritonic chemistry.

David Wellnitz, Guido Pupillo, Johannes Schachenmayer