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We explore excitonic energy transfer dynamics in a molecular dimer systemcoupled to both structured and unstructured oscillator environments. Byextending the reaction coordinate master equation technique developed in [J.Iles-Smith, N. Lambert, and A. Nazir, Phys. Rev. A 90, 032114 (2014)], we gobeyond the commonly used Born-Markov approximations to incorporatesystem-environment correlations and the resultant non-Markovian dynamicaleffects. We obtain energy transfer dynamics for both underdamped and overdampedoscillator environments that are in perfect agreement with the numericalhierarchical equations of motion over a wide range of parameters. Furthermore,we show that the Zusman equations, which may be obtained in a semiclassicallimit of the reaction coordinate model, are often incapable of describing thecorrect dynamical behaviour. This demonstrates the necessity of properlyaccounting for quantum correlations generated between the system and itsenvironment when the Born-Markov approximations no longer hold. Finally, weapply the reaction coordinate formalism to the case of a structured environmentcomprising of both underdamped (i.e. sharply peaked) and overdamped (broad)components simultaneously. We find that though an enhancement of the dimerenergy transfer rate can be obtained when compared to an unstructuredenvironment, its magnitude is rather sensitive to both the dimer-peak resonanceconditions and the relative strengths of the underdamped and overdampedcontributions.

Energy transfer in structured and unstructured environments: master equations beyond the Born-Markov approximations