Disorder enhanced vibrational entanglement and dynamics in polaritonic chemistry (2107.06053v2)

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.