构象和溶剂对酞菁锌-苯并吡啶三亚胺共轭物光诱导电子转移动力学的影响:非绝热动力学模拟。

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL
Sha-Sha Liu, Xin Wei, Yan Zheng, Shuai Liu, Dong-Hui Xu, Laicai Li, Ganglong Cui, Xiang-Yang Liu
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引用次数: 0

摘要

在此,我们采用线性响应时间相关密度泛函理论(LR-TDDFT)水平上的静态电子结构计算和非绝热动力学模拟,结合优化调谐范围分离混合(OT-RSH)函数,探索了酞菁锌-苯并吡啶三亚胺(ZnPc-BPTI)共轭物的超快光诱导动力学。由于连接体的灵活性,我们确定了两种主要构象:堆叠构象(ZnPc-BPTI-1)和扩展构象(ZnPc-BPTI-2)。由于 ZnPc-BPTI-1 中的电荷转移态远低于最低局域激发,这与 ZnPc-BPTI-2 相反,因此只有在 ZnPc 吸收最大值附近的局域激发时,才能在 ZnPc-BPTI-1 的非绝热模拟中观察到超快电子转移(约 3.6 ps)。然而,当考虑到苯甲腈中的溶剂效应时:对于不同的构象,最低 S1 态都是从 ZnPc 到 BPTI 的电荷转移态。随后的非绝热动力学模拟表明,两种构象在苯甲腈中都经历了超快电子转移,两个时间常数分别为 90 [100] fs 和 1.40 [1.43] ps。我们目前的工作不仅与之前的实验研究完全吻合,而且还指出了构象变化和溶剂效应在调节有机供体-受体共轭物光动力学中的重要作用。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Conformational and Solvent Effects on the Photoinduced Electron Transfer Dynamics of a Zinc Phthalocyanine-Benzoperylenetriimide Conjugate: A Nonadiabatic Dynamics Simulation.

Herein, we employed a combination of static electronic structure calculations and nonadiabatic dynamics simulations at linear-response time dependent density functional theory (LR-TDDFT) level with the optimally tuned range-separated hybrid (OT-RSH) functional to explore the ultrafast photoinduced dynamics of a zinc phthalocyanine-benzoperylenetriimide (ZnPc-BPTI) conjugate. Due to the flexibility of the linker, we identified two major conformations: the stacked conformation (ZnPc-BPTI-1) and the extended conformation (ZnPc-BPTI-2). Since the charge transfer states are much lower than the lowest local excitation in ZnPc-BPTI-1, which is contrary to ZnPc-BPTI-2, the ultrafast electron transfer (~3.6 ps) is only observed in the nonadiabatic simulations of ZnPc-BPTI-1 upon local excitation around the absorption maximum of ZnPc. However, when considering the solvent effects in benzonitrile: the lowest S1 states are both charge transfer states from ZnPc to BPTI for different conformers. Subsequent nonadiabatic dynamics simulations indicate that both conformers experience ultrafast electron transfer in benzonitrile with two time constants of 90 [100] fs and 1.40 [1.43] ps. Our present work not only agrees well with previous experimental study, but also points out the important role of conformational changes and solvent effects in regulating the photodynamics of organic donor-acceptor conjugates.

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来源期刊
Chemphyschem
Chemphyschem 化学-物理:原子、分子和化学物理
CiteScore
4.60
自引率
3.40%
发文量
425
审稿时长
1.1 months
期刊介绍: ChemPhysChem is one of the leading chemistry/physics interdisciplinary journals (ISI Impact Factor 2018: 3.077) for physical chemistry and chemical physics. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. ChemPhysChem is an international source for important primary and critical secondary information across the whole field of physical chemistry and chemical physics. It integrates this wide and flourishing field ranging from Solid State and Soft-Matter Research, Electro- and Photochemistry, Femtochemistry and Nanotechnology, Complex Systems, Single-Molecule Research, Clusters and Colloids, Catalysis and Surface Science, Biophysics and Physical Biochemistry, Atmospheric and Environmental Chemistry, and many more topics. ChemPhysChem is peer-reviewed.
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