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Vibronic absorption spectrum and electronic properties of azure C in aqueous solution: TD-DFT study

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Abstract

The vibronic absorption spectrum of Azure C (AC) in an aqueous solution is calculated using the time-dependent density functional theory (TD-DFT). The results of calculations are analyzed using all published hybrid functionals supported by Gaussian16, the 6–31 +  + G(d,p) basis set, and the IEFPCM and SMD solvent models. The solvent model IEFPCM gave significantly underestimated values of λmax in comparison with the experiment. This is a manifestation of the TD-DFT "cyanine failure". However, the SMD model made it possible to obtain a good agreement between the calculation results and experimental data. The best fit was achieved using the X3LYP functional. According to our calculations, the shoulder in the visible absorption spectrum of AC has a vibronic origin. The dipole moments and atomic charges of the ground and excited states of the AC molecule have been calculated. Photoexcitation leads to an increase in the dipole moment of the dye molecule. An insignificant photoinduced electron transfer was found in the central ring of the chromophore of the dye molecule. Following our results, the absorption peak of the AC solution in the visible region of the spectrum is due to the π → π* type electronic transition. Vibronic coupling plays a significant role in the absorption spectra of AC.

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Authors and Affiliations

  1. Physics Department, Nakhimov Black Sea Higher Naval School, Dybenko st.,1a, Sevastopol, Crimea, 299028

    Lyudmila O. Kostjukova & Svetlana V. Leontieva

  2. Physics Department, Sevastopol State University, Universitetskaya St., 33, Sevastopol, Crimea, 299053

    Victor V. Kostjukov

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Kostjukova, L.O., Leontieva, S.V. & Kostjukov, V.V. Vibronic absorption spectrum and electronic properties of azure C in aqueous solution: TD-DFT study. Theor Chem Acc 140, 114 (2021). https://doi.org/10.1007/s00214-021-02808-y

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