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Reduced density matrix hybrid approach: Application to electronic energy transfer

机译:降低密度矩阵混合方法:在电子能量转移中的应用

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Electronic energy transfer in the condensed phase, such as that occurring in photosynthetic complexes, frequently occurs in regimes where the energy scales of the system and environment are similar. This situation provides a challenge to theoretical investigation since most approaches are accurate only when a certain energetic parameter is small compared to others in the problem. Here we show that in these difficult regimes, the Ehrenfest approach provides a good starting point for a dynamical description of the energy transfer process due to its ability to accurately treat coupling to slow environmental modes. To further improve on the accuracy of the Ehrenfest approach, we use our reduced density matrix hybrid framework to treat the faster environmental modes quantum mechanically, at the level of a perturbative master equation. This combined approach is shown to provide an efficient and quantitative description of electronic energy transfer in a model dimer and the Fenna-Matthews-Olson complex and is used to investigate the effect of environmental preparation on the resulting dynamics.
机译:凝结相中的电子能量转移,例如发生在光合配合物中的能量转移,通常发生在系统和环境的能量规模相似的环境中。这种情况对理论研究提出了挑战,因为大多数方法仅在某个高能参数与问题中其他参数相比较小时才是准确的。在这里,我们表明,在这些困难的情况下,埃伦费斯特方法由于可以准确地处理与慢速环境模式耦合的能力,因此为动态描述能量转移过程提供了一个很好的起点。为了进一步提高Ehrenfest方法的准确性,我们使用了降低密度矩阵的混合框架,以扰动主方程的水平机械地处理了速度更快的环境模式。该组合方法显示出可对模型二聚体和Fenna-Matthews-Olson络合物中的电子能量转移进行高效和定量的描述,并用于研究环境准备对所得动力学的影响。

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