Cole Daniel J, Chin Alex W, Hine Nicholas D M, Haynes Peter D, Payne Mike C
†TCM Group, Cavendish Laboratory, 19 JJ Thomson Ave, Cambridge CB3 0HE, United Kingdom.
‡Department of Chemistry, Yale University, 225 Prospect Street, New Haven, Connecticut 06520-8107, United States.
J Phys Chem Lett. 2013 Dec 19;4(24):4206-12. doi: 10.1021/jz402000c. Epub 2013 Nov 27.
We present progress toward a first-principles parametrization of the Hamiltonian of the Fenna-Matthews-Olson pigment-protein complex, a molecule that has become key to understanding the role of quantum dynamics in photosynthetic exciton energy transfer. To this end, we have performed fully quantum mechanical calculations on each of the seven bacteriochlorophyll pigments that make up the complex, including a significant proportion of their protein environment (more than 2000 atoms), using linear-scaling density functional theory exploiting a recent development for the computation of excited states. Local pigment transition energies and interpigment coupling between optical transitions have been calculated and are in good agreement with the literature consensus. Comparisons between simulated and experimental optical spectra point toward future work that may help to elucidate important design principles in these nanoscale devices.
我们展示了在对费纳-马修斯-奥尔森色素-蛋白质复合体哈密顿量进行第一性原理参数化方面所取得的进展，该分子已成为理解量子动力学在光合激子能量转移中作用的关键。为此，我们利用线性标度密度泛函理论，对构成该复合体的七种细菌叶绿素色素中的每一种进行了全量子力学计算，其中包括其相当一部分蛋白质环境（超过2000个原子），该理论利用了最近在激发态计算方面的进展。已经计算了局部色素跃迁能量以及光学跃迁之间的色素间耦合，并且与文献共识高度吻合。模拟光谱与实验光谱之间的比较为未来的工作指明了方向，这可能有助于阐明这些纳米级器件中的重要设计原则。
