DFT/TDDFT Study on the Electronic Structure and Spectral Properties of Diphenyl Azafluoranthene Derivative |
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Authors: | P. Ga?siorski K. S. Danel M. Matusiewicz T. Uchacz W. Ku?nik A. V. Kityk |
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Affiliation: | (1) Faculty of Electrical Engineering, Czȩstochowa University of Technology, Al. Armii Krajowej 17, 42-200 Czȩstochowa, Poland;(2) Department of Chemistry, University of Agriculture, Balicka str. 122, 30-149 Krak?w, Poland;(3) Faculty of Chemistry, Jagiellonian University, Ingardena str. 3, 30-060 Krak?w, Poland;(4) Chemical Department, Silesian University of Technology, Strzody 9, Gliwice, Poland; |
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Abstract: | Paper reports the DFT/TDDFT study on the electronic structure and spectral properties of the five-membered annulated diphenyl azafluoranthene derivative 1,3-diphenyl-3H-indeno[1,2,3-de]pyrazolo[3,4-b]quinoline (DPIPQ) by means of polarizable continuum model (PCM) and Onsager reaction field approaches at the B3LYP/6-31+G(d,p) level of theory. The results of calculations are compared with the optical absorption and fluorescence spectra as well as with the cyclic voltammetry data. The DFT/TDDFT/PCM approaches exhibit rather good quantitative agreement regarding the spectral position of the first absorption band; the discrepancy between the experiment and theory is less than 0.06 eV (linear response approach) or 0.25 eV (state specific approach). As for the fluorescence emission the TDDFT/PCM calculations underestimate the transition energy on about of 0.7–0.8 eV. Such discrepancy should be attributed to insufficient quality of the TDDFT/PCM optimization in the excited state. Ignoring the geometrical relaxation in the excited state provides considerably better agreement between the experiment and theory; discrepancy is less than 0.1–0.22 eV depending on a solvent polarity. The dominant influence on the fluorescence emission results mainly from the solvent reorganization in the excited state whereas the solute relaxation is indeed weak and may be ignored. |
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