Molecule-photon interactions in phononic environments

Abstract

Molecules constitute compact hybrid quantum optical systems that can interface photons, electronic degrees of freedom, localized mechanical vibrations, and phonons. In particular, the strong vibronic interaction between electrons and nuclear motion in a molecule resembles the optomechanical radiation pressure Hamiltonian. While molecular vibrations are often in the ground state even at elevated temperatures, one still needs to get a handle on decoherence channels associated with phonons before an efficient quantum optical network based on optovibrational interactions in solid-state molecular systems could be realized. As a step towards a better understanding of decoherence in phononic environments, we take here an open quantum system approach to the nonequilibrium dynamics of guest molecules embedded in a crystal, identifying regimes of Markovian versus non-Markovian vibrational relaxation. A stochastic treatment, based on quantum Langevin equations, predicts collective vibron-vibron dynamics that resembles processes of sub- and super-radiance for radiative transitions. This in turn leads to the possibility of decoupling intramolecular vibrations from the phononic bath, allowing for enhanced coherence times of collective vibrations. For molecular polaritonics in strongly confined geometries, we also show that the imprint of optovibrational couplings onto the emerging output field results in effective polariton cross-talk rates for finite bath occupancies.