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Boranil and Related NBO Dyes: Insights From Theory

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journal contribution
posted on 19.02.2016, 04:02 by Siwar Chibani, Azzam Charaf-Eddin, Boris Le Guennic, Denis Jacquemin
The simulations of excited-state properties, that is, the 0–0 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, ωB97X-D, and ωB97) 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.