Energy transfer in structured and unstructured environments: Master equations beyond the Born-Markov approximations
- Controlled Quantum Dynamics Theory, Imperial College London, London SW7 2PG (United Kingdom)
- Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg (Germany)
- CEMS, RIKEN, Saitama 351-0198 (Japan)
- Photon Science Institute and School of Physics and Astronomy, The University of Manchester, Oxford Road, Manchester M13 9PL (United Kingdom)
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.
- OSTI ID:
- 22493683
- Journal Information:
- Journal of Chemical Physics, Vol. 144, Issue 4; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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