Signatures of coherent energy transfer and exciton delocalization in time-resolved optical cross correlations

Abstract

We investigate how optical second-order cross correlations witness the quantum features of a prototype donor-acceptor light-harvesting unit. By considering a pair of detuned two-level emitters electronically coupled and incoherently driven to a non-equilibrium steady-state, we gain insight into how electronic quantum properties such as exciton eigenstate delocalization, coherent energy transfer and steady-state electronic coherence, are manifested in the joint probability of emission or optical second-order cross correlation. Specifically, we show that the frequency associated with oscillations present in time-resolved second-order cross correlation functions quantifies not only the time scale of coherent energy transfer but also the degree of delocalization of the exciton eigenstates. Furthermore, we show that time-resolved cross correlations directly witness steady-state electronic coherence. Our work strengthens the idea that measurements of the intensity quantum cross correlations can provide distinctive signatures of the quantum behavior of biophysical emitters.