Relation between Nonlinear Optical Properties of Push鈥揚ull Molecules and Metric of Charge Transfer Excitations

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• 作者：Nanna Holmgaard List ; Robert Zale艣ny ; N. Arul Murugan ; Jacob Kongsted ; Wojciech Bartkowiak ; Hans 脜gren
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2015
• 出版时间：September 8, 2015
• 年：2015
• 卷：11
• 期：9
• 页码：4182-4188
• 全文大小：386K
• ISSN：1549-9626

文摘

We establish the relationships between the metric of charge transfer excitation (螖r) for the bright 蟺蟺* state and the two-photon absorption probability as well as the first hyperpolarizability for two families of push鈥損ull 蟺-conjugated systems. As previously demonstrated by Guido et al. (J. Chem. Theory Comput. 2013, 9, 3118鈥?126), 螖r is a measure for the average hole鈥揺lectron distance upon excitation and can be used to discriminate between short- and long-range electronic excitations. We indicate two new benefits from using this metric for the analyses of nonlinear optical properties of push鈥損ull systems. First, the two-photon absorption probability and the first hyperpolarizability are found to be interrelated through 螖r; if 尾 鈭?(螖r)^k, then roughly, 未^TPA 鈭?(螖r)^k+1. Second, a simple power relation between 螖r and the molecular hyperpolarizabilities of push鈥損ull systems offers the possibility of estimating properties for longer molecular chains without performing calculations of high-order response functions explicitly. We further demonstrate how to link the hyperpolarizabilities with the chain length of the push鈥損ull 蟺-conjugated systems through the metric of charge transfer.