Toyota Central Research and Development Laboratories, Inc., 41-1, Yokomichi, Nagakute, Aichi 480-1192, Japan.
Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, USA.
Phys Chem Chem Phys. 2018 Oct 10;20(39):25275-25294. doi: 10.1039/c8cp03841d.
We report a study on the non-adiabatic molecular dynamics (NA-MD) of the charge transfer (CT) process in the boron subphtalocyanine chloride (SubPc)/fullerene (C60) interface using our newly implemented Libra-X software package, which is based on an interface of the Libra NA-MD library and the GAMESS electronic structure software. In particular, we address the following aspects of the simulation protocol: (a) the choice of the potential used to treat interatomic interactions and its effect on the structures of the complex and CT rates; (b) the choice of the electronic structure methodology used; and (c) the choice of the trajectory surface hopping (TSH) methodology used. From our analysis of the electronic structure, we suggest that the distortion of the SubPc conical structure affects orbital localization and that the "breathing" motion of SubPc drives the CT process in SubPc/C60. This study illustrates that the choice of the TSH methodology and electronic decoherence are crucial for the CT simulation. We extend our analysis of CT in SubPc/(C60)n models by increasing the number of C60 molecules up to n = 4. We find that the details of the interfacial SubPc/(C60)n geometry determine the CT rate. Finally, we find the computed CT timescale to be in the range of 2.2-5.0 ps, which is in agreement with the experimentally determined timescale in the order of magnitude of ∼10 ps. The developed open-source Libra-X package is freely available on the Internet at https://github.com/Quantum-Dynamics-Hub/Libra-X.
我们报告了使用我们新实现的 Libra-X 软件包对硼次酞菁氯（SubPc）/富勒烯（C60）界面中的电荷转移（CT）过程进行非绝热分子动力学（NA-MD）的研究，该软件包基于 Libra NA-MD 库和 GAMESS 电子结构软件的接口。特别是，我们解决了模拟协议的以下方面：（a）用于处理原子间相互作用的势的选择及其对复合物结构和 CT 速率的影响；（b）电子结构方法的选择；（c）轨迹表面跳跃（TSH）方法的选择。从我们对电子结构的分析中，我们建议 SubPc 锥形结构的变形会影响轨道定位，并且 SubPc 的“呼吸”运动会驱动 SubPc/C60 中的 CT 过程。这项研究表明，TSH 方法和电子退相干的选择对于 CT 模拟至关重要。我们通过将 C60 分子的数量增加到 n = 4 来扩展我们对 SubPc/（C60）n 模型中的 CT 的分析。我们发现界面 SubPc/（C60）n 几何形状的细节决定了 CT 速率。最后，我们发现计算出的 CT 时间尺度在 2.2-5.0 ps 范围内，与实验确定的时间尺度在量级上约为 10 ps 一致。开发的开源 Libra-X 软件包可在互联网上的 https://github.com/Quantum-Dynamics-Hub/Libra-X 免费获得。
