Volume and heat of solution of hydrogen in rare earths from proton screening charges

In this work we determine some fundamental microscopic and macroscopic properties of rare earth-hydrogen (RE-H) systems. The behaviour of the electronic density variation of RE-H systems is obtained, using a program based on the density functional formalism. This information allows us to calculate the volume of solution of hydrogen in rare earths, as well as their heat of solution, and to compare with experimental results.     

Many-body effects in the optical absorption of lithium azide (LiN3)

Until recently most of the understanding achieved for solid explosives has been obtained using various semi-empirical approaches due to a major role of excitonic effects in the mechanisms of decomposition. Nevertheless, during the last two decades, thanks to the ongoing progress in iterative computational methods, the inclusion of the electron-hole interaction in ab initio calculations has become a standard approach in solid-state theory. In this paper, the electronic structure and optical properties of bulk lithium azide are investigated, taking into account the electron-hole interaction via the Bethe–Salpeter equation (BSE). Here, we employ the kernel polynomial method (KPM), which significantly reduces the computational cost compared to direct diagonalization methods. The calculations of the imaginary part of the polarization dependent dielectric function including excitonic effects are reported for the first time. Then, we show a density map of the two-particle wave function and propose an alternative interpretation of the initial stages of the externally triggered chemical decomposition, based on the analysis of two-particle states near the absorption edge.     

Electron correlation effects on magnetic Compton profiles of nickel in the GW approximation

The magnetic Compton profiles (MCPs) of 3d transition metal nickel are calculated by the GW approximation with FLAPW basis sets on the LSDA. The 3d valence band width narrowing, which is ascribed to the dynamical screening effects, contributes to eliminate an anomalous peak at 0.7 a.u. in the 〈110〉 direction, and also to diminish the excessive estimation of the Umklapp effects, in the LSDA MCPs. These are in good agreement with experimental observation.     

Energy expression of the chemical bond between atoms in metal oxides

The chemical bond between atoms in metal oxides is expressed in an energy scale. Total energy is partitioned into the atomic energy densities of constituent elements in the metal oxide, using energy density analysis. The atomization energies, ΔE_M for metal atom and ΔE_O for O atom, are then evaluated by subtracting the atomic energy densities from the energy of the isolated neutral atom, M and O, respectively. In this study, a ΔE_O vs. ΔE_M diagram called atomization energy diagram is first proposed and used for the understanding of the nature of chemical bond in various metal oxides. Both ΔE_M and ΔE_O values reflect the average structure as well as the local structure. For example their values vary depending on the vertex, edge or face sharing of MO₆ octahedron, and also change with the overall density of binary metal oxides. For perovskite-type oxides it is shown that the ΔE_O value tends to increase by the phase transition from cubic to tetragonal phase, regardless of the tilting-type or the 〈1 0 0〉 displacement-type transition. The bond formation in spinel-type oxides is also understood with the aid of the atomization energies. The present approach based on the atomization energy concept will provide us a new clue to the design of metal oxides.     

Formation of shallow acceptors in ZnO doped by lithium with the addition of nitrogen

We performed first-principle total-energy calculations to investigate the mechanism for the realization of high quality p-type ZnO codoped with lithium and nitrogen. We find that the higher hole concentrations measured in the codoped ZnO is related to decreased ionization energy of acceptors and reduction of compensations. The dual acceptor N_O-Li_Zn complex proposed in experiments is unstable. While in the (Li_I-N_O)-Li_Zn complex, where acceptor Li_Zn binds to the passivated (Li_I-N_O) complex is stable and acts as a single acceptor. The activation energy of this complex is about 60 meV lower than that of Li_Zn in Li-monodoped ZnO. The formation of inactive (Li_I-N_O) complexes creates a fully occupied impurity band just above the valence band maximum of ZnO. Thus Li atoms binding to this complex is activated by the electrons from the complex state rather than from the host states, accounting for decreased activation energy. Besides, Li_I⁺ and N_O⁻ bind tightly through the Coulomb interaction. Such binding will suppress the amount of compensating donor Li_I and limit the compensation for the desired acceptor Li_Zn.     

A DFT study of 5-fluorouracil adsorption on the pure and doped BN nanotubes

The electronic and adsorption properties of the pristine, Al-, Ga-, and Ge-doped BN nanotubes interacted with 5-fluorouracil molecule (5-FU) were theoretically investigated in the gas phase using the B3LYP density functional theory (DFT) calculations. It was found that the adsorption behavior of 5FU molecule on the pristine (8, 0) and (5, 5) BNNTs are electrostatic in nature. In contrast, the 5FU molecule (O-side) implies strong adsorption on the metal-doped BNNTs. Our results indicate that the Ga-doped presents high sensitivity and strong adsorption with the 5-FU molecule than the Al- and Ge-doped BNNTs. Therefore, it can be introduced as a carrier for drug delivery applications.     

Band structure calculations on the layered compounds FeGa2S4 and NiGa2S4

For the compounds FeGa₂S₄ and NiGa₂S₄ band structure calculations have been performed by the ab initio plane wave pseudo-potential method. The valence charge density distribution points to an ionic type of chemical bonding between the transition metal atoms and the ligand atoms. Two models for the pseudo-potentials are used to calculate the band structures: (a) only s and p electrons and (b) also the d-shells of the transition metal atoms are included in the pseudo-potentials. The differences between these two cases of band structures are discussed. Energy gap formation peculiarities are analysed for both crystals. Zak's elementary energy band concept is demonstrated for the energy spectra of the considered crystals.     

Linear and nonlinear optical properties of 3-nitroaniline (m-NA) and 4-nitroaniline (p-NA) crystals: A DFT/TDDFT study

We have studied the electronic structure and optical responses of 3-nitroaniline and 4-nitroaniline crystals within the framework of density functional theory (DFT). In addition, the excitonic effects are investigated by using the recently published bootstrap exchange-correlation kernel within the time dependent density functional theory (TDDFT) framework. Our calculations based on mBJ approximation yield the indirect band gap for both crystals, but the larger one for m-NA. Due to the excitonic effects, the TDDFT calculations gives rise to the enhanced and red-shifted spectra (compared to RPA). Due to the weak intermolecular interactions, band-structure calculations yield bands with low dispersion for both crystals. This study shows that the substituent groups play an important role in the top of valence band and the bottom of conduction band. Due to the linear structure of p-NA molecule, the highest peaks are located in the optical spectra of p-NA crystal, while m-NA has more sharp peaks, especially at lower energies. Both DFT and TDDFT calculations for the energy loss spectra show plasmon peaks around 27 and 28 eV for p-NA and m-NA, respectively. Due to the non-centrosymmetric structure of m-NA crystal, we also have reported its nonlinear spectra and the 2ω/ω intra-band and inter-band contributions to the dominant susceptibilities. Findings indicate the opposite signs for these contributions, especially at higher energies. The comparison between nonlinear spectra and the linear spectra (as a function of both ω and 2ω) reveals the significant resemblance between linear and nonlinear patterns. In addition to the reasonable agreement between our results with experimental data, this study reveals the spectral similarities between crystalline susceptibility and molecular polarizability.     

Effects of Stone-Wales Defect Symmetry on the Electronic Structure and Transport Properties of Narrow Armchair Graphene Nanoribbon

We report a first principles calculation to investigate the electron transport properties of defected armchair graphene nanoribbon (AGNR) influenced by Stone-Wales (SW) defect. The SW defect is found to be able to effectively influence the electronic structure of the defected AGNRs, and their electron transport behaviors can exhibit prominent differences depending on the symmetry of the nanostructured morphology. Moreover, our simulations have revealed that the introducing of the SW defect could be favorable for the electron transport of the defective AGNR. Our investigation has confirmed the possibility of tuning the electron transport of graphene nanoribbon by introducing a topological defect, which could be helpful to extending the field of applications for graphene nanoribbon-based nanodevices.     

Electric field gradients at 181Ta probe in ZrNi: Results from perturbed angular correlation and first-principles calculations

Results of temperature dependent perturbed angular correlation (PAC) measurements in the equiatomic ZrNi alloy have been reported for the first time using ¹⁸¹Hf probe. At room temperature, values of quadrupole frequency and asymmetry parameter for the major component (~80%) are found to be ω_Q=26.8(4) Mrad/s, and η=0.413(7). The resulting electric field gradient comes out to be V_zz=2.99 ×10¹⁷ V/cm² and this corresponds to the probe nuclei occupying the regular substitutional Zr sites. In ZrNi system, no magnetic interaction is observed down to 77 K indicating absence of any magnetism in this material. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) studies on an inactive but similarly prepared sample confirm the dominant presence of the orthorhombic ZrNi phase in the sample. A complementary density functional theory (DFT) calculation results in V_zz=−2.35×10¹⁷ V/cm², η=0.46 at the ¹⁸¹Ta probe impurity site and zero magnetic moment on each atomic site, in close agreement with the experimental results. Furthermore, it is found that electric field gradient for the regular component follows a T^3/2 temperature dependence between 77 and 353 K, beyond which it varies linearly with temperature.     

Type I FA (Rb, Cs) and II FA (Li, Na) tunable laser activities and donor-acceptor properties of O and O at KCl (001) surface: first principle calculations

Type I F_A (Rb⁺, Cs⁺) and II F_A (Li⁺, Na⁺) tunable laser activities, adsorptivity and donor-acceptor properties of O and O⁻ adsorbates at the flat surface of KCl crystal were investigated using an embedded cluster model and ab initio methods of molecular electronic structure calculations. Ion clusters were embedded in a simulated Coulomb field that closely approximates the Madelung field of the host surface, and the nearest neighbor ions to the defect site were allowed to relax to equilibrium. Based on the calculated Stokes shifted optical transition bands, F_A tunable laser activities were found to be inversely proportional to the size of the dopant cation (Li⁺, Na⁺, Rb⁺, Cs⁺) relative to the host cation (K⁺). This relation was explained in terms of the axial perturbation of the impurity cation. The probability of orientational bleaching attributed to the RES saddle point ion configuration along the 〈110〉 axis was found to be inversely proportional to the size of the dopant cation, with activation energy barriers of ca. 0.44-3.34 eV. Surface relaxation energies of type II F_A centers were more important than those of type I F_A centers. In terms of defect formation energies, the products of type II F_A center imperfection were more stable than those of type I F_A. The difference between F or F_A band energies and exciton bands depended almost exclusively on the size of the positive ion species. As far as the adsorptivity of O and O⁻ is concerned, the results confirm that surface imperfection enhances the adsorption energies by ca. 4.38-16.37 eV. O and O⁻ penetrate through the defect-containing surface. The energy gap between the adsorbate and the defect containing surface and the donor-acceptor property of adsorbate play the dominant role in the course of adsorbate substrate interactions and the results were explained in terms of electrostatic potential curves and Mulliken population analysis.     

First-principles investigation of the surface structures of Cu(n, n−1, 0) (n=2, 3 and 4) stepped surfaces

Multilayer relaxation at high-index Cu(n, n−1, 0) (n=2, 3 and 4) stepped surfaces was determined by the first-principles pseudopotential plane wave (PPPW) method. For those surfaces that have n and n−1 atom-rows in terrace and subterrace, respectively, the topmost 2n−2 interlayer spacings contract, while the 2n−1st interlayer spacing expands. There is no similar rule found for the relaxations parallel to the surfaces. Compared with the bulk terminated structure, a thin compact layer, which consisted of the topmost 2n−1 atom layers and separated slightly from the underneath atom layers, makes the surface more flat after relaxation. The bond-lengths between the step edge (first layer) atom and its nearest-neighbors do not depend on the surface termination, but only on the local coordination.     

Pressure effect on the electronic and optical properties of the alkali antimonide semiconductors Cs3Sb, KCs2Sb, CsK2Sb and K3Sb: Ab initio study

We present first principles calculations of the effect of pressure on the electronic and optical properties of the alkali antimonides semiconductors K₃Sb, K₂CsSb, KCs₂Sb and Cs₃Sb by means of the full-potential linearized augmented plane wave method within the generalized gradient approximation. The band gap variation is not linear. The crossover pressure values are determined for K₃Sb and K₂CsSb. Under pressure the structures in the optical spectra shift towards higher energies for K₃Sb and KCs₂Sb whereas the threshold energy is lowered for K₂CsSb and Cs₃Sb. The electronic dielectric constant decreases with pressure for K₃Sb while it increases for the other three compounds. Our results indicate that the absorption becomes strong in the UV region for KCs₂Sb and Cs₃Sb.     

The influence of oxygen vacancies on the electronic and magnetic properties of perovskite-like SrFeO3-x

The electronic, magnetic properties and lattice relaxations of oxygen-deficient cubic strontium ferrite, SrFeO_2.875, in ferromagnetic configuration are studied by means of the density functional theory using LCAO basis (SIESTA code) calculations. It is shown that Fe and Sr atoms are displaced from oxygen vacancies while oxygen anions are attracted to the vacancies. The DOS distributions, magnetic moments and atomic effective charges are analyzed in comparison with vacancy free SrFeO₃; these parameters are found to change weakly with appearance of oxygen vacancies, in contrast to conventional ionic picture. Some strengthening of Fe-O covalent bonds in the vicinity of the oxygen vacancy is found. The formation energy of oxygen vacancies and divacancies are evaluated.     

Doping-induced spin-manipulation in complex trimer system Ca3Cu3(PO4)4: A density functional investigation

Doping induced spin-manipulation with magnetic (Ni) and non-magnetic (Mg) dopants constitutes the experimental attempts to obtain a singlet ground state system from the linear chain Heisenberg antiferromagnetic Cu-based d⁹ spin-1/2 trimer compound Ca³Cu³(PO⁴)⁴ with doublet ground state. The present study is a density-functional investigation of the effects of such doping on the spin-exchange mechanism and electronic structure of the parent compound. Site-selective doping with zero-spin dopants like Mg is proved to be more efficient than an integral spin dopant Ni in obtaining a spin-gap system with singlet ground state, as also observed in the experimental studies. Doping induced dimerized state is found to be the lowest in ground-state energy. Calculated spin exchange couplings along various possible pathways are observed to attain good agreement with earlier experimental results with suitable optimization of Coulomb repulsion (U) and exchange (J) parameters.     

Trends in adsorption of open-shell atoms and small molecular fragments on the Ag(1 1 1) surface

The chemisorption of various atoms (C, N, O, Cl) and molecular fragments (OH, NH, CH, NH₂, CH₂) on the Ag(1 1 1) surface has been studied by employing the embedded cluster and multireference single- and double-excitation configuration interaction (MRD-CI) methods. Ground and excited states of the cluster-adsorbate systems have been computed and molecular orbitals (MOs) as well as electronic charge density distributions and Mulliken populations have been analyzed in order to extract general trends in chemisorption properties for different adsorbates. It has been found that the adsorbate-surface bond is energetically most favorable when a maximum of two electrons of the metal are shared with a given adsorbate. As a result atomic/molecular fragments with less than six valence electrons (N, CH, C) retain some open shells upon adsorption, whereas oxygen as well as chlorine isovalent species form a singlet ground state on the surface. All species considered except for Cl have mainly covalent bonding character to the surface, with an electronic charge of up to 1.0 transferred to the adsorbate from the silver cluster. It has been shown that the ionicity of the bond is strongly correlated with the electron affinity of the adsorbed species. Binding energies, equilibrium geometry and adsorbate location on the cluster have been computed and compared with available experimental data. In addition, the characteristic properties of chemisorption on Ag(1 1 1) and Pt(1 1 1) surfaces have been compared.     

Trends in stability, elastic and electronic properties of cubic Rh, Ir, Pd and Pt carbides depending on carbon content: MC versus M4C from first-principles calculations

First principles FLAPW-GGA calculations have been performed to understand the peculiarities of stability, elastic, electronic properties and chemical bonding for cubic carbides of four noble metals M=Rh, Pd, Ir and Pt depending on carbon stoichiometry: MC versus M₄C. Our main findings are as follows: (i) in contrast to mono-carbides MC with positive formation energies E_form>0, carbon-deficient sub-carbides M₄C are stable (E_form<0), thus carbon stoichiometry is one of the major factors determining successful synthesis of these materials, and (ii) as distinct from the majority of other 3d-5d metals (including Pd and Pt examined here), an unusual effect of Rh and Ir “metallization” and the increasing of ductility for these metals owing to the introduction of carbon has been established.     

Elastic, electronic, and optical properties of hypothetical SnNNi3 and CuNNi3 in comparison with superconducting ZnNNi3

The elastic, electronic, and optical properties of MNNi₃ (M=Zn, Sn, and Cu) have been calculated using the plane-wave ultrasoft pseudopotential technique, which is based on the first-principle density functional theory (DFT) with generalized gradient approximation (GGA). The optimized lattice parameters, independent elastic constants (C₁₁, C₁₂, and C₄₄), bulk modulus B, compressibility K, shear modulus G, and Poisson's ratio υ, as well as the band structures, total and atom projected densities of states and finally the optical properties of MNNi₃ have been evaluated and discussed. The electronic band structures of the two hypothetical compounds show metallic behavior just like the superconducting ZnNNi₃. Using band structures, the origin of features that appear in different optical properties of all the three compounds has been discussed. The large reflectivity of the predicted compounds in the low energy region might be useful in good candidate materials for coating to avoid solar heating.