Pereira Tamires Lima, Leal Luciano Almeida, da Cunha Wiliam Ferreira, Timóteo de Sousa Júnior Rafael, Ribeiro Junior Luiz Antonio, Antonio da Silva Filho Demétrio
Institute of Physics, University of Brasília, 70.919-970, Brasília, Brazil.
Department of Electrical Engineering, University of Brasília, CP04455, Brasília, DF, CEP 70919-970, Brazil.
J Mol Model. 2017 Mar;23(3):71. doi: 10.1007/s00894-017-3246-7. Epub 2017 Feb 15.
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.
通过密度泛函理论和含时密度泛函理论计算，我们对不同泛函方案对酞菁分子电子和光学性质的影响进行了全面研究。通过对OT-LC-BLYP/6-31G(d,p)泛函进行我们自己的调整，我们表明这样的过程对于准确匹配实验结果至关重要。我们将我们的结果与文献中其他几种结果进行了比较，包括B3LYP/6-31+G(d,p)组合，该组合通常被描述为获得带隙良好描述的最佳组合。这里获得的结果不仅表明光学性质相对于传统的BLYP有显著改善，而且就光学性质而言，与文献中的当前基准相比，我们还可以客观地报告我们调整后的泛函有改进。特别是，通过这种方法，可以在理论和实验光学带隙以及吸收光谱中主峰的位置之间实现良好的一致性。因此，我们的结果表明，通过调整过程校正库仑算符交换项中的长程项，是准确描述酞菁分子性质的一个好选择。
