Akimov Alexey V
Department of Chemistry, University at Buffalo, The State University of New York , Buffalo, New York 14260-3000, United States.
J Chem Theory Comput. 2016 Dec 13;12(12):5719-5736. doi: 10.1021/acs.jctc.6b00955. Epub 2016 Dec 1.
This work presents a nonadiabatic molecular dynamics methodology that relies on the use of fragment molecular orbitals computed using tight-binding Hamiltonians. The approach aims to model charge and energy transfer in large systems via quantum-classical trajectory-based approaches. The technique relies on a chemically motivated fragmentation of the overall system into arbitrary fragments. Several types of fragment molecular orbitals (FMO) can be constructed and used in nonadiabatic simulations, comprising quasidiabatic, adiabatic, and Löwdin-transformed ones. The adiabatic FMOs are found to be most suitable for modeling nonadiabatic dynamics in complex molecular systems. The overall algorithm shows advantageous scaling properties, making it possible to model long time scale charge transfer processes in large systems with many hundreds of atoms. The approach is applied to study charge transfer in subphtalocyanine(SubPc)/C heterojunction. The computational results emphasize the importance of decoherence and details of interfacial structure for obtaining accurate charge transfer time scales in SubPc/C herejunctions.
这项工作提出了一种非绝热分子动力学方法，该方法依赖于使用基于紧束缚哈密顿量计算的片段分子轨道。该方法旨在通过基于量子经典轨迹的方法对大型系统中的电荷和能量转移进行建模。该技术依赖于将整个系统基于化学原理分解为任意片段。可以构建几种类型的片段分子轨道（FMO）并用于非绝热模拟，包括准绝热、绝热和洛维丁变换的轨道。发现绝热FMO最适合于对复杂分子系统中的非绝热动力学进行建模。整体算法显示出有利的缩放特性，使得能够对具有数百个原子的大型系统中的长时间尺度电荷转移过程进行建模。该方法被应用于研究亚酞菁（SubPc）/C异质结中的电荷转移。计算结果强调了退相干和界面结构细节对于在此类SubPc/C异质结中获得准确电荷转移时间尺度的重要性。
