Schulze J, Kühn O
Institut für Physik, Universität Rostock, D-18051 Rostock, Germany.
J Phys Chem B. 2015 May 21;119(20):6211-6. doi: 10.1021/acs.jpcb.5b03928. Epub 2015 May 8.
The coupled exciton-vibrational dynamics of a three-site model of the Fenna-Matthews-Olson complex is investigated using the numerically exact multilayer multiconfiguration time-dependent Hartree approach. Thereby the specific coupling of the vibrational modes to local electronic transitions is adapted from a discretized experimental spectral density. The solution of the resulting time-dependent Schrödinger equation including three electronic and 450 vibrational degrees of freedom is analyzed in terms of excitonic populations and coherences. Emphasis is put onto the role of specific ranges of vibrational frequencies. It is observed that modes between 160 and 300 cm(-1) are responsible for the sub-picosecond population and coherence decay. Further, it is found that a mean-field approach with respect to the vibrational degrees of freedom is not applicable.
利用数值精确的多层多组态含时哈特里方法，研究了费纳 - 马修斯 - 奥尔森复合物三格点模型的激子 - 振动耦合动力学。由此，振动模式与局域电子跃迁的特定耦合取自离散化的实验光谱密度。对所得包含三个电子自由度和450个振动自由度的含时薛定谔方程的解，从激子布居数和相干性方面进行了分析。重点关注了特定振动频率范围的作用。观察到160至300厘米⁻¹之间的模式导致了亚皮秒级的布居数和相干性衰减。此外，还发现关于振动自由度的平均场方法并不适用。
