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Absorption spectra of azobenzenes simulated with time-dependent density functional theory

Authors

  • Denis Jacquemin,

    Corresponding author
    1. Unité de Chimie Physique Théorique et Structurale, University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
    Current affiliation:
    1. Laboratoire CEISAM, UMR 6230, 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3, France
    • Unité de Chimie Physique Théorique et Structurale, University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
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  • Julien Preat,

    1. Unité de Chimie Physique Théorique et Structurale, University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
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  • Eric A. Perpète,

    1. Unité de Chimie Physique Théorique et Structurale, University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
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  • Daniel P. Vercauteren,

    1. Unité de Chimie Physique Théorique et Structurale, University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
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  • Jean-Marie André,

    1. Unité de Chimie Physique Théorique et Structurale, University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
    2. Royal Academy of Belgium, Palais des Académies, Rue Ducale, 1, 1000 Bruxelles, Belgium
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  • Ilaria Ciofini,

    1. Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisations pour l'Energie, UMR CNRS n° 7575, ENSCP Chimie Paris Tech, 11, rue Pierre et Marie Curie, F-75321 Paris Cedex 05, France
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  • Carlo Adamo

    Corresponding author
    1. Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisations pour l'Energie, UMR CNRS n° 7575, ENSCP Chimie Paris Tech, 11, rue Pierre et Marie Curie, F-75321 Paris Cedex 05, France
    • Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisations pour l'Energie, UMR CNRS n° 7575, ENSCP Chimie Paris Tech, 11, rue Pierre et Marie Curie, F-75321 Paris Cedex 05, France
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Abstract

Using time-dependent density functional theory and the polarizable continuum model, we have simulated the absorption spectra of an extended series of azobenzene dyes. First, we have determined a theoretical level optimal for this important class of dyes, and it turned out that a C-PCM-CAM-B3LYP/6-311+G(d,p)//C-PCM-B3LYP/6-311G(d,p) approach represents an effective compromise between chemical accuracy and computational cost. In a second stage, we have compared the theoretical and experimental transition energies for 46 n → π and 141 π → π excitations. For the full set, that spans over a 302–565 nm domain, we obtained a mean absolute deviation of 13 nm (0.10 eV) and a linear correlation coefficient of 0.95, illustrating the accuracy of our approach, though some significant outliers pertained. In a last step, the impact of several modifications, that is, trans/cis isomerization, variation of the acidity of the medium and azo/hydrazo tautomerism have been modeled with two functionals. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010

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