MoO₃ and MoO₂ systems have attracted particular attention for many widespread applications thanks to their electronic and optical peculiarities; from the crystallographic point of view, MoO₃ adopts a thermodynamically stable orthorhombic phase (α-MoO₃) belonging to the space group Pbmn, while MoO₂ assumes a monoclinic arrangement characterized by space group P2₁/c. In the present paper, we investigated the electronic and optical properties of both MoO₃ and MoO₂ by using Density Functional Theory calculations, in particular, the Meta Generalized Gradient Approximation (MGGA) SCAN functional together with the PseudoDojo pseudopotential, which were used for the first time to obtain a deeper insight into the nature of different Mo–O bonds in these materials. The calculated density of states, the band gap, and the band structure were confirmed and validated by comparison with already available experimental results, while the optical properties were validated by recording optical spectra. Furthermore, the calculated band-gap energy value for the orthorhombic MoO₃ showed the best match to the experimental value reported in the literature. All these findings suggest that the newly proposed theoretical techniques reproduce the experimental evidence of both MoO₂ and MoO₃ systems with high accuracy.

Tungsten diselenide WSe₂ is a material with an intriguing character that has captivated the attention of researchers; in this study, an ab initio analysis is presented that focuses on the optical and electronic properties of WSe₂.

HfO₂ can assume different crystalline structures, such as monoclinic, orthorhombic, and cubic polymorphs, each one characterized by unical properties. The peculiarities of this material are also strongly related to the presence of doping elements in the unit cell. Thus, the present paper has the main purpose of studying and comparing twelve different systems characterized by diverse polymorphs and doping percentages. In particular, three different crystalline structures were considered: the monoclinic P2₁/c, the orthorhombic Pca2₁, and the cubic Fm$\overline{3}$m phases of HfO₂. Each one has been studied by using Y as a doping agent with three different contents: 0% Y:HfO₂, 8% Y:HfO₂, 12% Y:HfO₂, and 16% Y:HfO₂. For all the systems, density functional theory (DFT) methods based on PBE/GGA, and on the HSE hybrid functionals were used to optimize the geometry as well as to study their optical properties. Depending on the polymorphs, Y affects the formation energy in different ways and causes changes in the optical properties. When the percentage of Y did not exceed 12%, a stabilization of the cubic phase fraction and an increase of the dielectric constant was observed. Additionally, the calculated optical bandgap energies and the refractive index are examined to provide an overview of the systems and are compared with experimental data. The bandgaps obtained are in perfect agreement with the experimental values and show a slight increase as the doping percentage grows, while only minor differences are found between the three polymorphs in terms of both refractive index and optical band gap. The adopted first principles study generates a reasonable prediction of the physical-chemical properties of all the systems, thus identifying the effects of doping phenomena.

We have studied the structural, electronic, magnetic, and optical properties of the VO ₂ (B) polymorph using first-principles calculations based on density functional theory (DFT).

By means of different spectroscopic techniques, we investigate a novel series of porphyrin derivatives (H₂TPP), connected to dibenzo-24-crown-8 (DB24C8) moieties, which undergo self-assembly with different methano[60]fullerene units bearing dibenzylammonium (DBA) cations. The formation of both [2] and [3]pseudorotaxanes was proved by means of NMR, UV-Vis-NIR absorption and emission spectroscopies. With the support of molecular modelling studies, spectroscopic investigations showed the presence of a secondary interaction between the porphyrin and the C₆₀ chromophores leading to the formation of different types of “face-to-face” assemblies. Remarkably, investigations of the non-linear optical response of these supramolecular systems showed that individual porphyrin and fullerene derivatives exhibit significantly lower second hyperpolarizability values when compared to their pseudorotaxanes functionalised counterparts. This proves that this class of supramolecular materials possesses relevant NLO response, which strongly depends on the structural arrangement of the chromophores in solution.