From atomistic modeling to excitation transfer and two-dimensional spectra of the FMO light-harvesting complex.
From atomistic modeling to excitation transfer and two-dimensional spectra of the FMO light-harvesting complex.
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DOI：
10.1021/jp202619a
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发表时间：
2011-07-07
影响因子：
3.3
通讯作者：
Kleinekathoefer, Ulrich
中科院分区：
文献类型：
--
作者：
Olbrich, Carsten;Jansen, Thomas L. C.;Liebers, Joerg;Aghtar, Mortaza;Struempfer, Johan;Schulten, Klaus;Knoester, Jasper;Kleinekathoefer, Ulrich
低温下 Fenna-Matthews-Olson (FMO) 光捕获复合体中长寿命量子相干性的实验观察挑战了复杂分子系统领域的一般直觉，并引发了寻找解释的大量理论努力。在这里，我们结合分子动力学模拟和电子结构计算，报告了 FMO 中激发态动力学的室温计算。因此，我们获得了该系统的哈密顿量轨迹，其中包含单个细菌叶绿素分子的时间依赖性垂直激发能及其相互电子耦合。能量和耦合的分布以及可能的空间相关性被分析。研究发现，与常见的假设相反，站点能量分布是非高斯分布的。在后续步骤中，使用平均波包动力学来确定系统中的激子动力学。最后，确定与时间相关的哈密顿线性谱和二维谱。由此获得的线性吸收线形与实验观察非常吻合，并且很大程度上由非高斯位点能量分布决定。二维光谱与根据较低温度下的实验观察结果推断的结果一致，并且表明长寿命相干性几乎完全丧失。
The experimental observation of long-lived quantum coherences in the Fenna-Matthews-Olson (FMO) light-harvesting complex at low temperatures has challenged general intuition in the field of complex molecular systems and provoked considerable theoretical effort in search for explanations. Here we report on room-temperature calculations of the excited-state dynamics in FMO using a combination of molecular dynamics simulations and electronic structure calculations. Thus we obtain trajectories for the Hamiltonian of this system which contains time-dependent vertical excitation energies of the individual bacteriochlorophyll molecules and their mutual electronic couplings. The distribution of energies and couplings are analyzed together with possible spatial correlations. It is found that in contrast to frequent assumptions the site energy distribution is non-Gaussian. In a subsequent step, averaged wave packet dynamics is used to determine the exciton dynamics in the system. Finally, with the time-dependent Hamiltonian linear and two-dimensional spectra are determined. The thus obtained linear absorption lineshape agrees well with experimental observation and is largely determined by the non-Gaussian site energy distribution. The two-dimensional spectra are in line with what one would expect by extrapolation of the experimental observations at lower temperatures and indicate almost total loss of long-lived coherences.
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影响因子：
4.4
作者：
Dijkstra, Arend G.;Jansen, Thomas La Cour;Knoester, Jasper
通讯作者：
Knoester, Jasper
影响因子：
2.8
作者：
deBoeij, WP;Pshenichnikov, MS;Wiersma, DA
通讯作者：
Wiersma, DA
影响因子：
3.4
作者：
Adolphs, Julia;Renger, Thomas
通讯作者：
Renger, Thomas
影响因子：
2.4
作者：
Damjanovic, A;Kosztin, I;Schulten, K
通讯作者：
Schulten, K
影响因子：
4.4
作者：
Jansen, T. L. C.;Auer, B. M.;Skinner, J. L.
通讯作者：
Skinner, J. L.