Electronic excitation dynamics in multichromophoric systems described via a polaron-representation master equation
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- Avinash Kolli
- University College London 1 Department of Physics and Astronomy, , Gower Street, London WC1E 6BT, United Kingdom
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- Ahsan Nazir
- University College London 1 Department of Physics and Astronomy, , Gower Street, London WC1E 6BT, United Kingdom
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- Alexandra Olaya-Castro
- University College London 1 Department of Physics and Astronomy, , Gower Street, London WC1E 6BT, United Kingdom
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説明
<jats:p>We derive a many-site version of the non-Markovian time-convolutionless polaron master equation [Jang et al., J. Chem Phys. 129, 101104 (2008)]10.1063/1.2977974 to describe electronic excitation dynamics in multichromophoric systems. By treating electronic and vibrational degrees of freedom in a combined frame (polaron frame), this theory is capable of interpolating between weak and strong exciton-phonon coupling and is able to account for initial non-equilibrium bath states and spatially correlated environments. Besides outlining a general expression for the expected value of any electronic system observable in the original frame, we also discuss implications of the Markovian and Secular approximations highlighting that they need not hold in the untransformed frame despite being strictly satisfied in the polaron frame. The key features of the theory are illustrated using as an example a four-site subsystem of the Fenna-Mathews-Olson light-harvesting complex. For a spectral density including a localised mode, we show that oscillations of site populations may only be observed when non-equilibrium bath effects are taken into account. Furthermore, we illustrate how this formalism allows us to identify the electronic and vibrational components of the oscillatory dynamics.</jats:p>
収録刊行物
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- The Journal of Chemical Physics
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The Journal of Chemical Physics 135 (15), 154112-, 2011-10-20
AIP Publishing