Shuai Zhigang, Li Weitang, Ren Jiajun, Jiang Yuqian, Geng Hua
MOE Key Laboratory of Organic OptoElectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, 100084 Beijing, People's Republic of China.
Laboratory for Nanosystem and Hierarchy Fabrication, National Center for Nanoscience and Technology, Chinese Academy of Sciences, 100084 Beijing, People's Republic of China.
J Chem Phys. 2020 Aug 28;153(8):080902. doi: 10.1063/5.0018312.
Marcus theory has been successfully applied to molecular design for organic semiconductors with the aid of quantum chemistry calculations for the molecular parameters: the intermolecular electronic coupling V and the intramolecular charge reorganization energy λ. The assumption behind this is the localized nature of the electronic state for representing the charge carriers, being holes or electrons. As far as the quantitative description of carrier mobility is concerned, the direct application of Marcus semiclassical theory usually led to underestimation of the experimental data. A number of effects going beyond such a semiclassical description will be introduced here, including the quantum nuclear effect, dynamic disorder, and delocalization effects. The recently developed quantum dynamics simulation at the time-dependent density matrix renormalization group theory is briefly discussed. The latter was shown to be a quickly emerging efficient quantum dynamics method for the complex system.
借助对分子参数（分子间电子耦合V和分子内电荷重组能λ）的量子化学计算，马库斯理论已成功应用于有机半导体的分子设计。其背后的假设是，用于表示电荷载流子（空穴或电子）的电子态具有局域性。就载流子迁移率的定量描述而言，直接应用马库斯半经典理论通常会导致对实验数据的低估。这里将引入一些超出这种半经典描述的效应，包括量子核效应、动态无序和离域效应。简要讨论了最近在含时密度矩阵重整化群理论下发展起来的量子动力学模拟。后者被证明是一种快速兴起的用于复杂系统的高效量子动力学方法。
