Identifying Differences between Semiclassical and Full-Quantum Descriptions of Plexcitons

Strong light-matter coupling between molecules and plasmonic nanoparticles gives rise to new hybrid eigenstates of the coupled system, commonly referred to as polaritons or, more precisely, plexcitons. Over the past decade, it has been amply shown that molecular electron dynamics and photophysics can be drastically affected by such interactions, thus paving the way for light-induced control of molecular excited state properties and reactivity. Here, by combining the ab initio molecular description and classical or quantum modeling of arbitrarily shaped plasmonic nanostructures within the stochastic Schrödinger equation, we present two approaches, one semiclassical and one full-quantum, to follow in real time the electronic dynamics of plexcitons while realistically taking plasmonic dissipative losses into account. The full-quantum theory is compared with the semiclassical analogue under different interaction regimes, showing (numerically and theoretically) that even in the weak-field and weak-coupling limit a small-yet-observable difference arises.