Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States.
Department of Chemistry, University of California, Berkeley, California 94720, United States.
J Chem Theory Comput. 2022 Jul 12;18(7):4095-4108. doi: 10.1021/acs.jctc.2c00163. Epub 2022 Jun 22.
The recently introduced multisite tensor network path integral (MS-TNPI) allows simulation of extended quantum systems coupled to dissipative media. We use MS-TNPI to simulate the exciton transport and the absorption spectrum of a B850 bacteriochlorophyll (BChl) ring. The MS-TNPI network is extended to account for the ring topology of the B850 system. Accurate molecular-dynamics-based description of the molecular vibrations and the protein scaffold is incorporated through the framework of Feynman-Vernon influence functional. To relate the present work with the excitonic picture, an exploration of the absorption spectrum is done by simulating it using approximate and topologically consistent transition dipole moment vectors. Comparison of these numerically exact MS-TNPI absorption spectra are shown with second-order cumulant approximations. The effect of temperature on both the exact and the approximate spectra is also explored.
最近提出的多点张量网络路径积分（MS-TNPI）允许模拟与耗散介质耦合的扩展量子系统。我们使用 MS-TNPI 来模拟激子输运和 B850 细菌叶绿素（BChl）环的吸收光谱。MS-TNPI 网络扩展到可以考虑 B850 系统的环拓扑结构。通过费曼-弗农影响函数的框架，将基于分子动力学的分子振动和蛋白质支架的精确描述结合起来。为了将目前的工作与激子图像联系起来，通过使用近似和拓扑一致的跃迁偶极矩矢量来模拟吸收光谱来进行探索。将这些数值上精确的 MS-TNPI 吸收光谱与二阶累积量近似进行比较。还研究了温度对精确和近似光谱的影响。
