Optimally tuned functionals improving the description of optical and electronic properties of the phthalocyanine molecule

Abstract

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.

Molecular Reactivity and Absorption Properties of Melanoidin Blue-G1 through Conceptual DFT

“…Various TDDFT studies of different sizes of molecules have used the optimally-tuned RSH density functionals. The studies report that absorption properties improve especially when applying the charge-transfer phenomenon [ 51 , 82 , 83 , 84 , 85 , 86 , 87 , 88 , 89 , 90 , 91 , 92 , 93 , 94 , 95 , 96 , 97 , 98 , 99 , 100 ].…”

Methodological Survey of Simplified TD-DFT Methods for Fast and Accurate Interpretation of UV–Vis–NIR Spectra of Phthalocyanines

“…A series of different exchange-correlation functionals were corrected, including a pure generalized gradient approximation (GGA)BP86, , hybrid GGAsB3LYP and TPSSh, meta-GGAM06, and range-separated hybridsCAM-B3LYP, LC-BLYP, and ωB97X . These functionals have been widely used to carry out TD-DFT calculations of tetrapyrrolic macrocycles, − and the benefits and drawbacks of their applications have been highlighted.…”

Conceptual DFT Study of the Local Chemical Reactivity of the Colored BISARG Melanoidin and Its Protonated Derivative

“…Thus, in this computational study we will assess eight density functionals in calculating the molecular properties and structure of the BISARG intermediate melanoidin pigment and its protonated derivative, BISARG(p). Following the same ideas of previous works, we will consider fixed RSH functional instead of the optimally-tuned RSH density functionals that have attained great success and have also supported the validity of the IP theorem in the context of the GKS theory (Stein et al, 2009a , b ; Karolewski et al, 2011 ; Kuritz et al, 2011 ; Refaely-Abramson et al, 2011 ; Foster and Wong, 2012 ; Koppen et al, 2012 ; Kronik et al, 2012 ; Phillips et al, 2012a , b ; Karolewski et al, 2013 ; Moore and Autschbach, 2013 ; Egger et al, 2014 ; Foster et al, 2014 ; Jacquemin et al, 2014 ; Niskanen and Hukka, 2014 ; Sun and Autschbach, 2014 ; Manna et al, 2015 ; Lima et al, 2016 ; Pereira et al, 2017 ).…”