_{4}revealed by ab initio calculations.

*J Phys Condens Matter ; 32(2): 025505, 2019 Oct 03.*

##### RESUMO

YbMgGaO4 was recently proposed as a promising quantum-spin-liquid candidate material. However, some details of its structure, such as those related to a spatial anisotropy, were not completely understood. In this work, we perform ab initio calculations based on density-functional-theory to investigate the structural, the electronic and the magnetic properties of YbMgGaO4. The geometrical model was constructed to take into account disorder effects produced by the random distribution of Ga and Mg along the lattice. We found a substantial spatial anisotropy revealed by variations up to 8% in the Mg-O and Ga-O bond lengths, which results in variations up to 3% in the Yb-Yb distances along its triangular lattice. Thus, the Yb lattice was not perfectly triangular. Furthermore, we demonstrate an out-of-plane magnetization at the Yb atoms with magnetic anisotropy energy of [Formula: see text] eV/Yb and a small interlayer exchange of [Formula: see text] eV/Yb, demonstrating that the system is only approximately two-dimensional. The presented results provide insights for an atomic-scale understanding of YbMgGaO4 with density-functional-theory calculations.

*Phys Chem Chem Phys ; 21(41): 23076-23084, 2019 Oct 24.*

##### RESUMO

An improved atomistic understanding of the W-based two-dimensional transition-metal dichalcogenides (2D TMDs) is crucial for technological applications of 2D materials, since the presence of tungsten endows these materials with distinctive properties. However, our atomistic knowledge on the evolution of the structural, electronic, and energetic properties and on the nanoflake stability of such materials is not properly addressed hitherto. Thus, we present a density functional theory (DFT) study of stoichiometric (WQ2)n nanoflakes, with Q = S, Se, Te, and n = 1, ,16, 36, 66, and 105. We obtained the configurations with n = 1, ,16 through the tree growth algorithm whereas the nanoflakes with n = 36, 66, and 105 were generated from fragments of 2D TMDs with an abundant diversity of shapes and edge configurations. We found that all the most stable nanoflakes present the same Q-terminated edge configuration. Furthermore, in isomers with n = 1, ,16 sizes, nanoflakes with triangular shapes and their derivatives, such as the rhombus geometry, define magic numbers, whereas for n > 16, triangular shapes were also found for the most stable structures, because they preserve the edge configuration. A strong modulation of the Hirshfeld charges, depending on chalcogen species and core or edge position, is also observed. The modulation of the Hirshfeld charge due to the nature of the W metal atoms makes the energetic 1D â 1T' transition of (WQ2)n differ in nanoflake size in relation to (MoQ2)n nanoflakes. Our analysis shows the interplay between edge configuration, coordination environment, and shape that determines the stability of nanoflakes, and allows us to describe design principles for stable 1T' stoichiometric nanoflakes of various sizes.

*Phys Chem Chem Phys ; 21(44): 24584-24591, 2019 Nov 28.*

##### RESUMO

The electronic transport properties in molecular heterojunctions are intimately connected with the molecular conformation between the electrodes, and the electronic structure of the molecule/electrode interface. In this work, we perform an ab initio density-functional-theory investigation of the structural and transport properties through self-assembled CuPc molecules sandwiched between gold contacts with (111) surfaces. We demonstrated (i) a tunneling regime ruled by the π orbitals of the aromatic rings of CuPc molecules; and (ii) a high variation (up to two orders of magnitude) of the current density with the orientation of the CuPc molecules relative to the gold surface. The source of this variation is the geometrical dependence of the energy of the highest-occupied-molecular-orbital with respect to the chemical potential of the metal and the generation of intra-molecular transport channels for a configuration with CuPc molecules tilted with respect to the gold surface.

*Phys Chem Chem Phys ; 21(21): 11359-11366, 2019 Jun 07.*

##### RESUMO

Transition metal dichalcogenides (TMDCs) are promising materials for applications in nanoelectronics and correlated fields, where their metallic edge states play a fundamental role in the electronic transport. In this work, we investigate the transport properties of MoS2 zigzag nanoribbons under a butadiene (C4H6) atmosphere, as this compound has been used to obtain MoS2 flakes by exfoliation. We use density functional theory combined with non-equilibrium Green's function techniques, in a methodology contemplating disorder and different coverages. Our results indicate a strong modulation of the TMDC electronic transport properties driven by butadiene molecules anchored at their edges, producing the suppression of currents due to a backscattering process. Our results indicate a high sensitivity of the TMDC edge states. Thus, the mechanisms used to reduce the dimensionality of MoS2 considerably modify its transport properties.

*ACS Appl Mater Interfaces ; 11(1): 1529-1537, 2019 Jan 09.*

##### RESUMO

Tuning the magnetic properties of materials is a demand of several technologies; however, our microscopic understanding of the process that drives the enhancement of those properties is still unsatisfactory. In this work, we combined experimental and theoretical techniques to investigate the handling of magnetic properties of FeCo thin films via the thickness-tuning of a gold film used as an underlayer. We grow the samples by the deposition of polycrystalline FeCo thin films on the Au underlayer at room temperature by a magnetron sputtering technique, demonstrating that the lattice parameter of the sub-20 nm thickness gold underlayer is dependent on its thickness, inducing a stress up to 3% in sub-5 nm FeCo thin films deposited over it. Thus, elastic-driven variations for the in-plane magnetic anisotropy energy, Ku, up to 110% are found from our experiments. Our experimental findings are in excellent agreement with ab initio quantum chemistry calculations based on density functional theory, which helps to build up an atomistic understanding of the effects that take place in the tuning of the magnetic properties addressed in this work. The handling mechanism reported here should be applied to other magnetic films deposited on different metallic underlayers, opening possibilities for large-scale fabrication of magnetic components to be used in future devices.

*Nanotechnology ; 29(7): 075703, 2018 Feb 16.*

##### RESUMO

The synthesis of silicon nanotubes realized in the last decade demonstrates multi-walled tubular structures consisting of Si atoms in [Formula: see text] and the [Formula: see text] hybridizations. However, most of the theoretical models were elaborated taking as the starting point [Formula: see text] structures analogous to carbon nanotubes. These structures are unfavorable due to the natural tendency of the Si atoms to undergo [Formula: see text]. In this work, through ab initio simulations based on density functional theory, we investigated double-walled silicon nanotubes proposing layered tubes possessing most of the Si atoms in an [Formula: see text] hybridization, and with few [Formula: see text] atoms localized at the outer wall. The lowest-energy structures have metallic behavior. Furthermore, the possibility to tune the band structure with the application of a strain was demonstrated, inducing a metal-semiconductor transition. Thus, the behavior of silicon nanotubes differs significantly from carbon nanotubes, and the main source of the differences is the distortions in the lattice associated with the tendency of Si to make four chemical bonds.

*J Chem Phys ; 126(14): 144107, 2007 Apr 14.*

##### RESUMO

We explore and compare three approximate schemes allowing simple implementation of complex density functionals by making use of self-consistent implementation of simpler functionals: (i) post-local-density approximation (LDA) evaluation of complex functionals at the LDA densities (or those of other simple functionals) (ii) application of a global scaling factor to the potential of the simple functional, and (iii) application of a local scaling factor to that potential. Option (i) is a common choice in density-functional calculations. Option (ii) was recently proposed by Cafiero and Gonzalez [Phys. Rev. A 71, 042505 (2005)]. We here put their proposal on a more rigorous basis, by deriving it, and explaining why it works, directly from the theorems of density-functional theory. Option (iii) is proposed here for the first time. We provide detailed comparisons of the three approaches among each other and with fully self-consistent implementations for Hartree, local-density, generalized-gradient, self-interaction corrected, and meta-generalized-gradient approximations, for atoms, ions, quantum wells, and model Hamiltonians. Scaled approaches turn out to be, on average, better than post approaches, and unlike these also provide corrections to eigenvalues and orbitals. Scaled self-consistency thus opens the possibility of efficient and reliable implementation of density functionals of hitherto unprecedented complexity.