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

Jake Iles-Smith, Arend G. Dijkstra, Neill Lambert, Ahsan Nazir

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    Abstract

    We explore excitonic energy transfer dynamics in a molecular dimer system coupled to both structured and unstructured oscillator environments. By extending the reaction coordinate master equation technique developed by Iles-Smith et al. [Phys. Rev. A 90, 032114 (2014)], we go beyond the commonly used Born-Markov approximations to incorporate system-environment correlations and the resultant non-Markovian dynamical effects. We obtain energy transfer dynamics for both underdamped and overdamped oscillator environments that are in perfect agreement with the numerical hierarchical equations of motion over a wide range of parameters. Furthermore, we show that the Zusman equations, which may be obtained in a semiclassical limit of the reaction coordinate model, are often incapable of describing the correct dynamical behaviour. This demonstrates the necessity of properly accounting for quantum correlations generated between the system and its environment when the Born-Markov approximations no longer hold. Finally, we apply the reaction coordinate formalism to the case of a structured environment comprising of both underdamped (i.e., sharply peaked) and overdamped (broad) components simultaneously. We find that though an enhancement of the dimer energy transfer rate can be obtained when compared to an unstructured environment, its magnitude is rather sensitive to both the dimer-peak resonance conditions and the relative strengths of the underdamped and overdamped contributions. (C) 2016 AIP Publishing LLC.
    Original languageEnglish
    Article number044110
    JournalJournal of Chemical Physics
    Volume144
    Issue number4
    Number of pages14
    ISSN0021-9606
    DOIs
    Publication statusPublished - 2016

    Keywords

    • Energy transfer
    • Friction
    • Partial differential equations
    • Rotational correlation time
    • Population dynamics

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