An ab initio simulation of the UV/visible spectra of N-benzylideneaniline dyes

Authors

  • Denis Jacquemin,

    Corresponding author
    1. Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, rue de Bruxelles, 61, B-5000 Namur, Belgium
    • Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, rue de Bruxelles, 61, B-5000 Namur, Belgium
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  • Adèle D. Laurent,

    1. Equipe de Chimie et Biochimie Théoriques, UMR 7565 CNRS-UHP, Institut Jean Barriol, (FR CNRS 2843), Faculté des Sciences et Techniques, Nancy-Université, B.P. 70329, 54506 Vandoeuvre-lès-Nancy, France
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  • Eric A. Perpète,

    1. Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, rue de Bruxelles, 61, B-5000 Namur, Belgium
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  • Jean-Marie André

    Corresponding author
    1. Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, rue de Bruxelles, 61, B-5000 Namur, Belgium
    2. Royal Academy of Belgium, Palais des Académies, Rue Ducale 1, B-1000 Bruxelles, Belgium
    • Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, rue de Bruxelles, 61, B-5000 Namur, Belgium
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Abstract

The structural parameters and the absorption spectra of more than thirty N-benzylideneaniline dyes have been determined with a theoretical scheme combining the time-dependent density functional theory and the polarizable continuum model. For the unsubstituted molecule, the PBE0 hybrid nicely reproduces both the measured structural parameters and the absorption spectrum, and we demonstrate that the nature of the two first transitions is reversed compared with azobenzene. For the set of substituted compounds, the average TD-DFT error (0.19 eV), that can be significantly reduced by a simple statistical treatment, mainly originates in the charge-transfer states of push–pull derivatives, whereas local transitions are accurately modeled. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009

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