Optimally tuned functionals improving the description of optical and electronic properties of the phthalocyanine molecule
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By means of Density functional theory and time-dependent density functional theory calculations, we present a comprehensive investigation on the influence of different functional schemes on electronic and optical properties of the phthalocyanine molecule. By carrying out our own tuning on the OT-LC-BLYP/6-31G(d,p) functional, we show that such a procedure is fundamental to accurately match experimental results. We compare our results to several others available in the literature, including the B3LYP/6-31+G(d,p) set, which is commonly portrayed as the best combination in order to obtain a good description of the band gap. The results obtained here present not only significant improvement of the optical properties from the conventional BLYP, but we can also objectively report an improvement of our tuned functional when compared to the current benchmark of the literature as far as optical properties are concerned. Particularly, by means of this approach, it was possible to achieve a good agreement between the theoretical and experimental optical gap as well as of the positioning of the main peaks in the absorption spectrum. Our results thus suggest that correcting the long-range term on exchange term of the Coulomb operator, by means of a tuning procedure, is a good option to accurately describe properties of the phthalocyanine molecule.
KeywordsDFT UV-Vis Phthalocyanine molecule Optical gap Excited states Oscillator strength
The authors gratefully acknowledge the financial support from Brazilian Research Councils CNPq, CAPES, FAP-DF, and FINATEC and CENAPAD-SP for providing the computational facilities. D.A.S.F. gratefully acknowledges the financial support from the Brazilian Research Council CNPq, grant 306968/2013-4 and FAP-DF grant 0193.001.062/2015. L.A.R.J. gratefully acknowledges the financial support from the Brazilian Research Council FAP-DF grant 0193.000942/2015. The authors R.T.S.J. and L.A.R.J. wish to thank the Brazilian Ministry of Planning, Budget and Management (Grant DIPLA 005/2016).
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