Electronic excitation dynamics in multichromophoric systems described via a polaron-representation master equation
| Autor: | Avinash Kolli, Ahsan Nazir, Alexandra Olaya-Castro |
|---|---|
| Rok vydání: | 2011 |
| Předmět: |
Photosynthetic Reaction Center Complex Proteins
General Physics and Astronomy Markov process FOS: Physical sciences Electrons Expected value Polaron 01 natural sciences symbols.namesake 0103 physical sciences Master equation Mesoscale and Nanoscale Physics (cond-mat.mes-hall) Physical and Theoretical Chemistry 010306 general physics Electronic systems Physics Quantum Physics 010304 chemical physics Condensed Matter - Mesoscale and Nanoscale Physics Spectral density Observable 3. Good health Classical mechanics Energy Transfer Models Chemical symbols Quantum Theory Quantum Physics (quant-ph) Excitation Algorithms |
| Zdroj: | The Journal of chemical physics. 135(15) |
| ISSN: | 1089-7690 |
| Popis: | We derive a many-site version of the non-Markovian time-convolutionless polaron master equation [S. Jang et al., J. Chem Phys. 129, 101104 (2008)] 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-Mathew-Olson light-harvesting complex. For a spectral density including a localised high-energy 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 or vibrational origin of the oscillatory dynamics. 13 pages, 6 figures; minor corrections made; accepted for publication in Journal of Chemical Physics |
| Databáze: | OpenAIRE |
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