Department of Chemistry, University of California, Berkeley, California 94720, USA.
J Phys Chem B. 2011 May 19;115(19):6227-33. doi: 10.1021/jp112406h. Epub 2011 Apr 13.
The observation of long-lived electronic quantum coherence in a photosynthetic light harvesting system [Engel et al. Nature 2007, 446, 782] has led to much effort being devoted to elucidation of the quantum mechanisms of the photosynthetic excitation energy transfer. In this paper we examine the question of whether the decay of the coherent beating signal is due to quantum mechanical decoherence or ensemble dephasing (also called "fake decoherence"). We compare results based on the quantum master equation description of the time-evolution of the reduced density matrix with a mixed quantum/classical approach where the ensemble average is calculated after the dynamics. The two methods show good agreement with results from the quantum master equation in terms of the decay of quantum coherent oscillations when ensemble average is considered for the mixed quantum/classical approach. However, the results also demonstrate it remains possible that the quantum coherent motion is robust under individual realizations of the environment-induced fluctuations contrary to intuition obtained from the reduced density matrices, indicating that the decay of the observed quantum coherence should be understood as ensemble dephasing. Our calculations imply that coherence is a property of the pigment-protein system, not simply the preparation method of the electronic excitation.
在光合作用光捕获系统中观察到长寿命的电子量子相干[Engel 等人,自然 2007,446,782],这促使人们致力于阐明光合作用激发能量转移的量子机制。在本文中,我们研究了相干拍频信号的衰减是由于量子力学退相干还是系综去相位(也称为“假退相干”)的问题。我们将基于量子主方程描述的约化密度矩阵的时间演化的结果与混合量子/经典方法进行了比较,其中在动力学之后计算系综平均值。这两种方法在考虑混合量子/经典方法中的系综平均时,与量子主方程的结果在量子相干振荡的衰减方面具有很好的一致性。然而,结果也表明,与从约化密度矩阵获得的直觉相反,在环境诱导波动的单个实现下,量子相干运动仍然可能是稳健的,这表明观察到的量子相干性的衰减应该被理解为系综去相位。我们的计算表明,相干性是色素-蛋白体系的一个特性,而不仅仅是电子激发的制备方法。