Boranil and Related NBO Dyes: Insights From Theory

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• 作者：Siwar Chibani ; Azzam Charaf-Eddin ; Boris Le Guennic ; Denis Jacquemin
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2013
• 出版时间：July 9, 2013
• 年：2013
• 卷：9
• 期：7
• 页码：3127-3135
• 全文大小：494K
• 年卷期：v.9,no.7(July 9, 2013)
• ISSN：1549-9626

文摘

The simulations of excited-state properties, that is, the 0鈥? energies and vibronic shapes, of a large panel of fluorophores presenting a NBO atomic sequence have been achieved with a Time-Dependent Density Functional Theory (TD-DFT) approach. We have combined eight hybrid exchange-correlation functionals (B3LYP, PBE0, M06, BMK, M06-2X, CAM-B3LYP, 蠅B97X-D, and 蠅B97) to the linear-response (LR) and the state specific (SS) Polarizable Continuum Model (PCM) methods in both their equilibrium (eq) and nonequilibrium (neq) limits. We show that the combination of the SS-PCM scheme to a functional incorporating a low amount of exact exchange can yield unphysical values for molecules presenting large increase of their dipole moments upon excitation. We therefore apply a functional possessing a large exact exchange ratio to simulate the properties of NBO dyes, including large dyads.