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A time‐convolutionless master equation approach for computing state‐to‐state rates was developed in which the coupling between states depends on the nuclear coordinates. This approach incorporates a fully quantum‐mechanical treatment of both the nuclear and electronic degrees of freedom and recovers the well‐known Marcus expression in the semiclassical limit. A significant breakthrough was made in using this approach by tying it to a fully ab initio quantum chemical approach for determining the diabatic states and electron‐phonon coupling terms, allowing unprecedented accuracy and utility for computing state‐to‐state electronic transition rates. The Weinstein group at the University of Sheffield reported recently upon a series of donor‐bridge‐acceptor (DBA) molecular triads whose electron‐transfer (ET) pathways can be radically changed by infrared light excitation of specific intramolecular vibrations. Once the diabatic states and couplings are determined, the TCLME approach is used to compute the time‐correlation functions and state‐to‐state golden‐rule rates. 

We present an input/output analysis of photon-correlation experiments whereby a quantum mechanically entangled bi-photon state interacts with a material sample placed in one arm of a Hong–Ou–Mandel apparatus. We show that the output signal contains detailed information about subsequent entanglement with the microscopic quantum states in the sample. In particular, we apply the method to an ensemble of emitters interacting with a common photon mode within the open-system Dicke model. Our results indicate considerable dynamical information concerning spontaneous symmetry breaking can be revealed with such an experimental system.