Domínguez-Castro Adrian, Frauenheim Thomas
Bremen Center for Computational Materials Science (BCCMS), Universität Bremen, Germany.
Phys Chem Chem Phys. 2021 Aug 28;23(32):17129-17133. doi: 10.1039/d1cp02890a. Epub 2021 Aug 6.
Theoretical calculations are an effective strategy to complement and understand the experimental results in atomistic detail. Ehrenfest molecular dynamics simulations based on the real-time time-dependent density functional tight-binding (RT-TDDFTB) approach are performed to reveal for the first time the electron dynamics for the charge separation of pyrene-functionalized middle-sized AuS(PH) and large-sized AuS(PR) (R = H, CH, CH, CH) clusters. The proposed mechanism uncovers an ultrafast and irreversible photoinduced charge transfer from the gold nanocluster (GNC) unit to the pyrene derivative in all cases. By a Fourier transform analysis of the dynamics, the effect of vibronic couplings is highlighted. The AuS(PPh)PPhPyr system exhibits the best performance for charge separation.
理论计算是一种有效的策略，可用于在原子细节上补充和理解实验结果。基于实时含时密度泛函紧束缚（RT-TDDFTB）方法进行了埃伦费斯特分子动力学模拟，首次揭示了芘功能化的中等尺寸AuS(PH)和大尺寸AuS(PR)（R = H、CH、CH、CH）团簇电荷分离的电子动力学。所提出的机制揭示了在所有情况下从金纳米团簇（GNC）单元到芘衍生物的超快且不可逆的光诱导电荷转移。通过对动力学进行傅里叶变换分析，突出了振子耦合的影响。AuS(PPh)PPhPyr系统在电荷分离方面表现出最佳性能。
