Long-range energy transport in photosystem II.

We simulate the long-range inter-complex electronic energy transfer in photosystem II-from the antenna complex, via a core complex, to the reaction center-using a non-Markovian (ZOFE) quantum master equation description that allows the electronic coherence involved in the energy transfer to be explicitly included at all length scales. This allows us to identify all locations where coherence is manifested and to further identify the pathways of the energy transfer in the full network of coupled chromophores using a description based on excitation probability currents. We investigate how the energy transfer depends on the initial excitation-localized, coherent initial excitation versus delocalized, incoherent initial excitation-and find that the overall energy transfer is remarkably robust with respect to such strong variations of the initial condition. To explore the importance of vibrationally enhanced transfer and to address the question of optimization in the system parameters, we systematically vary the strength of the coupling between the electronic and the vibrational degrees of freedom. We find that the natural parameters lie in a (broad) region that enables optimal transfer efficiency and that the overall long-range energy transfer on a ns time scale appears to be very robust with respect to variations in the vibronic coupling of up to an order of magnitude. Nevertheless, vibrationally enhanced transfer appears to be crucial to obtain a high transfer efficiency, with the latter falling sharply for couplings outside the optimal range. Comparison of our full quantum simulations to results obtained with a "classical" rate equation based on a modified-Redfield/generalized-Förster description previously used to simulate energy transfer dynamics in the entire photosystem II complex shows good agreement for the overall time scales of excitation energy transport.

Probability-current analysis of energy transport in open quantum systems.

We introduce a probability-current analysis of excitation energy transfer between states of an open quantum system. Expressing the energy transfer through currents of excitation probability between the states in a site representation enables us to gain key insights into the energy transfer dynamics. In particular, the analysis yields direct identification of the pathways of energy transport in large networks of sites and quantifies their relative weights, as well as the respective contributions of unitary dynamics, coherence, dephasing, and relaxation and dissipation processes to the energy transfer. It thus provides much more information than studying only excitation probabilities of the states as a function of time. Our analysis is general and can be readily applied to a broad range of dynamical descriptions of open quantum system dynamics with coupling to non-Markovian or Markovian environments.