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In this work, ab initio density functional theory calculations were performed in order to study the structural and electronic properties of halogens (X = fluorine, chlorine, bromine or iodine) that were deposited on both sides of graphene single layers (X-graphene). The adsorption of these atoms on only one side of the layer with hydrogen atoms adsorbed on the other was also considered (H,X-graphene). The results indicate that the F-C bond in the F-graphene system causes an sp(2) to sp(3) transition of the carbon orbitals, and similar effects seem to occur in the H,X-graphene systems. For the other cases, two configurations are found: bonded (B) and non-bonded (NB). For the B configuration, the structural arrangement of the atoms was similar to F-graphene and H-graphene (graphane), although the electronic structures present some differences. In the NB configuration, the interaction between the adsorbed atoms and the graphene layer seems to be essentially of the van der Waals type. In these cases, the original shape of the graphene layer presents only small deviations from the pristine form and the adsorbed atoms reach equilibrium far from the sheet. The F-graphene structure has a direct bandgap of approximately 3.16 eV at the Γ point, which is a value that is close to the value of 3.50 eV that was found for graphane. The Cl-graphene (B configuration), H,F-graphene and H,Cl-graphene systems have smaller bandgap values. All of the other systems present metallic behaviours. Energy calculations indicate the possible stability of these X-graphene layers, although some considerations about the possibility of spontaneous formation have to be taken into account.

Two-dimensional (2D) binary XBi compounds, where X belongs to group III elements (B, Al, Ga, and In), in a buckled honeycomb structure may originate sizable gap Z2 topological insulators (TIs). These are characterized by exhibiting single band inversion at the Γ point as well as nontrivial edge states in their corresponding nanoribbons. By using first-principles calculations, we demonstrate that hydrogenation of XBi single layers leads to distinct and stable crystal structures, which can preserve their topological insulating properties. Moreover, hydrogenation opens a band gap in this new class of 2D Z2 TIs, with distinct intensities, exhibiting an interesting electronic behavior for viable room-temperature applications of these 2D materials. The nature of the global band gap (direct or indirect) and topological insulating properties depend on the X element type and spatial configuration of the sheet, as well as the applied strain. Our results indicate that the geometric configuration can be crucial for preserving totally the topological characteristics of the hydrogenated sheets. We identify sizable band inversions in the band structure for the relaxed hydrogenated GaBi and InBi in their chairlike configurations and for hydrogenated BBi and AlBi under strain. Based on these findings, hydrogenation gives rise to a flexible chemical tunability and can preserve the band topology of the pristine XBi phases

We have investigated, using first-principles calculations, the energetic stability and structural properties of antisites, vacancies and substitutional carbon defects in a boron nitride monolayer. We have found that the incorporation of a carbon atom substituting for one boron atom, in an N-rich growth condition, or a nitrogen atom, in a B-rich medium, lowers the formation energy, as compared to antisites and vacancy defects. We also verify that defects, inducing an excess of nitrogen or boron, such as N(B) and B(N), are more stable in its reverse atmosphere, i.e. N(B) is more stable in a B-rich growth medium, while B(N) is more stable in a N-rich condition. In addition we have found that the formation energy of a C(N), in a N-rich medium, and C(B) in a B-rich medium, present formation energies comparable to those of the vacancies, V(N) and V(B), respectively.

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We have investigated the structure, adsorption, electronic states, and charge transfer of small water aggregates on the surface of a graphene layer using density functional theory. Our calculations were focused on water adsorbates containing up to five water molecules interacting with one and both sides of a perfect freestanding sheet. Different orientations of the aggregates with respect to the graphene sites were considered. The results show that the adsorption energy of one water molecule is primarily determined by its orientation, although it is also strongly dependent on the implemented functional scheme. Despite its intrinsic difficulties with dispersion interactions, the Perdew and Wang's exchange-correlation functional may be a viable alternative to investigate the adsorption of large molecular aggregates on a graphene surface. Although water physisorption is expected to occur in the regime of droplets, we found no induced impurity states close to the Fermi level of graphene interacting with small water clusters. In order to investigate the donor/acceptor tendency of the water clusters on graphene, we have performed a Bader charge analysis. Considering the charge transfer mechanism, we have noticed that it should preferentially occur from water to graphene only when the oxygen atom is pointing toward the surface. Otherwise, and in the case of larger adsorbed clusters, charge transfers systematically occur from graphene to water.

Abstract. Theoretical calculations focused on the stability of an infinite hexagonal AlN (h-AlN) sheet and its structural and electronic properties were carried out within the framework of DFT at the GGA-PBE level of theory. For the simulations, an h-AlN sheet model system consisting in 96 atoms per super-cell has been adopted. For h-AlN, we predict a lattice parameter of 1.82 Å and an indirect gap of 2.81 eV as well as a cohesive energy which is by 6% lower than that of the bulk (wurtzite) AlN which can be seen as a qualitative indication for synthesizability of individual h-AlN sheets. Besides the study of a perfect h-AlN sheet also the most typical defects, namely, vacancies, anti-site defects and impurities were also explored. The formation energies for these defects were calculated together with the total density of states and the corresponding projected states were also evaluated. The charge density in the region of the defects was also addressed. Energetically, the anti-site defects are the most costly, while the impurity defects are the most favorable, especially so for the defects arising from Si impurities. Defects such as nitrogen vacancies and Si impurities lead to a breaking of the planar shape of the h-AlN sheet and in some cases to formation of new bonds. The defects significantly change the band structure in the vicinity of the Fermi level in comparison to the band structure of the perfect h-AlN which can be used for deliberately tailoring the electronic properties of individual h-AlN sheets.2

This work investigates, using first-principles calculations, electronic and structural properties of hydrogen, lithium, sodium, potassium and rubidium that are adsorbed, in a regular pattern, on a graphene surface. The results for H-graphene (graphane) and Li-graphene were compared with previous calculations. The present results do not support previous claims that the Li-C bond in such a layer would result in an sp(2) to an sp(3) transition of carbon orbitals, being more compatible with some ionic character for the covalent bond and with lithium acting as an electron acceptor in a bridging environment. Calculations were also performed for the Na, K, and Rb-graphene systems, resulting in a similar electronic behaviour but with a more pronounced ionic character than for Li-graphene. Energy calculations indicate the possible stability of such ad-graphene layers, with only the Li-graphene being possible to be spontaneously obtained.