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Qualitative Identification of Carboxylic Acids, Boronic Acids, and Amines Using Cruciform Fluorophores
Published on: August 19, 2013
Boranil and Related NBO Dyes: Insights From Theory
Siwar Chibani1, Azzam Charaf-Eddin1, Boris Le Guennic2
1Laboratoire CEISAM, UMR CNR 6230, Université de Nantes , 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France.
Abstract:
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.
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