Antiferromagnetism with spin polarization of GaN-based diluted magnetic semiconductors

The diluted magnetic semiconductors are promising materials for spintronic applications. Usually one intents to find the ferromagnetic state but recently the antiferromagnetism (AFM) was proposed to have some advantages. In this work, we verify the possibility to obtain spin polarization with an AFM state. In particular, we studied GaN 5% double doped with two different transition metals atoms (Mn and Co or Cr and Ni), forming the Mn(x)Co(0.056-x)Ga(0.944)N and Cr(x)Ni(0.056-x)Ga(0.944)N quaternary alloys. In order to simulate these systems in a more realistic way, and take into account composition fluctuations, we adapted the generalized quasichemical approach to diluted alloys, which is used in combination with spin density-functional theory. We find that is possible to obtain an AFM ground state up to 70% spin polarization.

Theory of nitride oxide adsorption on transition metal (111) surfaces: a first-principles investigation

In this work, we report a density functional theory study of nitric oxide (NO) adsorption on close-packed transition metal (TM) Rh(111), Ir(111), Pd(111) and Pt(111) surfaces in terms of adsorption sites, binding mechanism and charge transfer at a coverage of Theta(NO) = 0.25, 0.50, 0.75 monolayer (ML). Based on our study, an unified picture for the interaction between NO and TM(111) and site preference is established, and valuable insights are obtained. At low coverage (0.25 ML), we find that the interaction of NO/TM(111) is determined by an electron donation and back-donation process via the interplay between NO 5 sigma/2 pi* and TM d-bands. The extent of the donation and back-donation depends critically on the coordination number (adsorption sites) and TM d-band filling, and plays an essential role for NO adsorption on TM surfaces. DFT calculations shows that for TMs with high d-band filling such as Pd and Pt, hollow-site NO is energetically the most favorable, and top-site NO prefers to tilt away from the normal direction. While for TMs with low d-band filling (Rh and Ir), top-site NO perpendicular to the surfaces is energetically most favorable. Electronic structure analysis show that irrespective of the TM and adsorption site, there is a net charge transfer from the substrate to the adsorbate due to overwhelming back-donation from the TM substrate to the adsorbed NO molecules. The adsorption-induced change of the work function with respect to bare surfaces and dipole moment is however site dependent, and the work function increases for hollow-site NO, but decreases for top-site NO, because of differences in the charge redistribution. The interplay between the energetics, lateral interaction and charge transfer, which is element dependent, rationalizes the structural evolution of NO adsorption on TM(111) surfaces in the submonolayer regime.

Accurate band gaps of AlGaN, InGaN, and AlInN alloys calculations based on LDA-1/2 approach

We present parameter-free calculations of electronic properties of InGaN, InAlN, and AlGaN alloys. The calculations are based on a generalized quasichemical approach, to account for disorder and composition effects, and first-principles calculations within the density functional theory with the LDA-1/2 approach, to accurately determine the band gaps. We provide precise results for AlGaN, InGaN, and AlInN band gaps for the entire range of compositions, and their respective bowing parameters. (C) 2011 American Institute of Physics. [doi:10.1063/1.3576570]

Theoretical investigation of atomic and electronic structures of Ga(2)O(3)(ZnO)(6)

Transparent conducting oxides (TCO) are widely used in technological applications ranging from photovoltaics to thin-film transparent field-effect transistors. In this work we report a first-principles investigation, based on density-functional theory, of the atomic and electronic properties of Ga(2)O(3)(ZnO)(6) (GZO(6)), which is a promising candidate to be used as host oxide for wide band gap TCO applications. We identify a low-energy configuration for the coherent distribution of the Ga and Zn atoms in the cation positions within the experimentally reported orthorhombic GZO(6) structure. Four Ga atoms are located in four-fold sites, while the remaining 12 Ga atoms in the unit cell form four shared Ga agglomerates (a motif of four atoms). The Zn atoms are distributed in the remaining cation sites with effective coordination numbers from 3.90 to 4.50. Furthermore, we identify the natural formation of twin-boundaries in GZO(6), which can explain the zigzag modulations observed experimentally by high-resolution transmission electron microscopy in GZO(n) (n=9). Due to the intrinsic twin-boundary formation, polarity inversion in the ZnO tetrahedrons is present which is facilitated by the formation of the Ga agglomerates. Our analysis shows that the formation of fourfold Ga sites and Ga agglomerates are stabilized by the electronic octet rule, while the distribution of Ga atoms and the formation of the twin-boundary help alleviate excess strain. Finally we identify that the electronic properties of GZO(6) are essentially determined by the electronic properties of ZnO, i.e., there are slight changes in the band gap and optical absorption properties.

Atomistic origins of the phase transition mechanism in Ge(2)Sb(2)Te(5)

The fast and reversible phase transition mechanism between crystalline and amorphous phases of Ge(2)Sb(2)Te(5) has been in debate for several years. Through employing first-principles density functional theory calculations, we identify a direct structural link between the metastable crystalline and amorphous phases. The phase transition is driven by the displacement of Ge atoms along the rocksalt [111] direction from stable octahedron to high energy unstable tetrahedron sites close to the intrinsic vacancy regions, which generates a high energy intermediate phase between metastable and amorphous phases. Due to the instability of Ge at the tetrahedron sites, the Ge atoms naturally shift away from those sites, giving rise to the formation of local-ordered fourfold motifs and the long-range structural disorder. Intrinsic vacancies, which originate from Sb(2)Te(3), lower the energy barrier for Ge displacements, and hence, their distribution plays an important role in the phase transition. The high energy intermediate configuration can be obtained experimentally by applying an intense laser beam, which overcomes the thermodynamic barrier from the octahedron to tetrahedron sites. The high figure of merit of Ge(2)Sb(2)Te(5) is achieved from the optimal combination of intrinsic vacancies provided by Sb(2)Te(3) and the instability of the tetrahedron sites provided by GeTe.

Low-energy electron scattering from methanol and ethanol

Measured and calculated differential cross sections for elastic (rotationally unresolved) electron scattering from two primary alcohols, methanol (CH(3)OH) and ethanol (C(2)H(5)OH), are reported. The measurements are obtained using the relative flow method with helium as the standard gas and a thin aperture as the collimating target gas source. The relative flow method is applied without the restriction imposed by the relative flow pressure conditions on helium and the unknown gas. The experimental data were taken at incident electron energies of 1, 2, 5, 10, 15, 20, 30, 50, and 100 eV and for scattering angles of 5 degrees-130 degrees. There are no previous reports of experimental electron scattering differential cross sections for CH(3)OH and C(2)H(5)OH in the literature. The calculated differential cross sections are obtained using two different implementations of the Schwinger multichannel method, one that takes all electrons into account and is adapted for parallel computers, and another that uses pseudopotentials and considers only the valence electrons. Comparison between theory and experiment shows that theory is able to describe low-energy electron scattering from these polyatomic targets quite well.

Dissipation as a mechanism of energy gain

Some properties of the annular billiard under the presence of weak dissipation are studied. We show, in a dissipative system, that the average energy of a particle acquires higher values than its average energy of the conservative case. The creation of attractors, associated with a chaotic dynamics in the conservative regime, both in appropriated regions of the phase space, constitute a generic mechanism to increase the average energy of dynamical systems.

Transition-metal 13-atom clusters assessed with solid and surface-biased functionals

First-principles density-functional theory studies have reported open structures based on the formation of double simple-cubic (DSC) arrangements for Ru(13), Rh(13), Os(13), and Ir(13), which can be considered an unexpected result as those elements crystallize in compact bulk structures such as the face-centered cubic and hexagonal close-packed lattices. In this work, we investigated with the projected augmented wave method the dependence of the lowest-energy structure on the local and semilocal exchange-correlation (xc) energy functionals employed in density-functional theory. We found that the local-density approximation (LDA) and generalized-gradient formulations with different treatment of the electronic inhomogeneities (PBE, PBEsol, and AM05) confirm the DSC configuration as the lowest-energy structure for the studied TM(13) clusters. A good agreement in the relative total energies are obtained even for structures with small energy differences, e. g., 0.10 eV. The employed xc functionals yield the same total magnetic moment for a given structure, i.e., the differences in the bond lengths do not affect the moments, which can be attributed to the atomic character of those clusters. Thus, at least for those systems, the differences among the LDA, PBE, PBEsol, and AM05 functionals are not large enough to yield qualitatively different results. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3577999]

The role of electron localization in the atomic structure of transition-metal 13-atom clusters: the example of Co(13), Rh(13), and Hf(13)

The crystalline structure of transition-metals (TM) has been widely known for several decades, however, our knowledge on the atomic structure of TM clusters is still far from satisfactory, which compromises an atomistic understanding of the reactivity of TM clusters. For example, almost all density functional theory (DFT) calculations for TM clusters have been based on local (local density approximation-LDA) and semilocal (generalized gradient approximation-GGA) exchange-correlation functionals, however, it is well known that plain DFT fails to correct the self-interaction error, which affects the properties of several systems. To improve our basic understanding of the atomic and electronic properties of TM clusters, we report a DFT study within two nonlocal functionals, namely, the hybrid HSE (Heyd, Scuseria, and Ernzerhof) and GGA + U functionals, of the structural and electronic properties of the Co(13), Rh(13), and Hf(13) clusters. For Co(13) and Rh(13), we found that improved exchange-correlation functionals decrease the stability of open structures such as the hexagonal bilayer (HBL) and double simple-cubic (DSC) compared with the compact icosahedron (ICO) structure, however, DFT-GGA, DFT-GGA + U, and DFT-HSE yield very similar results for Hf(13). Thus, our results suggest that the DSC structure obtained by several plain DFT calculations for Rh(13) can be improved by the use of improved functionals. Using the sd hybridization analysis, we found that a strong hybridization favors compact structures, and hence, a correct description of the sd hybridization is crucial for the relative energy stability. For example, the sd hybridization decreases for HBL and DSC and increases for ICO in the case of Co(13) and Rh(13), while for Hf(13), the sd hybridization decreases for all configurations, and hence, it does not affect the relative stability among open and compact configurations.

A microscopic view of substitution reactions solvated by ionic liquids

The solvation effect of the ionic liquid 1-N-butyl-3-methylimidazolium hexafluorophosphate on nucleophilic substitution reactions of halides toward the aliphatic carbon of methyl p-nitrobenzenesulfonate (pNBS) was investigated by computer simulations. The calculations were performed by using a hybrid quantum-mechanical/molecular-mechanical (QM/MM) methodology. A semiempirical Hamiltonian was first parametrized on the basis of comparison with ab initio calculations for Cl(-) and Br(-) reaction with pNBS at gas phase. In condensed phase, free energy profiles were obtained for both reactions. The calculated reaction barriers are in agreement with experiment. The structure of species solvated by the ionic liquid was followed along the reaction progress from the reagents, through the transition state, to the final products. The simulations indicate that this substitution reaction in the ionic liquid is slower than in nonpolar molecular solvents proper to significant stabilization of the halide anion by the ionic liquid in comparison with the transition state with delocalized charge. Solute-solvent interactions in the first solvation shell contain several hydrogen bonds that are formed or broken in response to charge density variation along the reaction coordinate. The detailed structural analysis can be used to rationalize the design of new ionic liquids with tailored solvation properties. (c) 2008 American Institute of Physics.

Chemiluminescence-based uphill energy conversion

The conversion of red excitation light into blue emission light (uphill energy conversion) using unstable 1,2-dioxetanes is described. The method is based on 1,2-dioxetane formation by red-light sensitized photooxygenation of adequate alkenes and subsequent blue-light emission due to thermal 1,2-dioxetane cleavage. The energy gain resulting from the chemical energy obtained in the transformation of an alkene into two carbonyl compounds transforms a red-light excitation laser beam into a blue-light chemiluminescence emission, producing thereby a formal anti-Stokes shift of 200-250 nm, opening up a whole spectrum of possible applications.

Full-dimensional analytical ab initio potential energy surface of the ground state of HOI

Extensive ab initio calculations using a complete active space second-order perturbation theory wavefunction, including scalar and spin-orbit relativistic effects with a quadruple-zeta quality basis set were used to construct an analytical potential energy surface (PES) of the ground state of the [H, O, I] system. A total of 5344 points were fit to a three-dimensional function of the internuclear distances, with a global root-mean-square error of 1.26 kcal mol(-1). The resulting PES describes accurately the main features of this system: the HOI and HIO isomers, the transition state between them, and all dissociation asymptotes. After a small adjustment, using a scaling factor on the internal coordinates of HOI, the frequencies calculated in this work agree with the experimental data available within 10 cm(-1). (C) 2011 American Institute of Physics. [doi: 10.1063/1.3615545]

Structure, stability, depolarized light scattering, and vibrational spectra of fullerenols from all-electron density-functional-theory calculations

We have investigated the stability, electronic properties, Rayleigh (elastic), and Raman (inelastic) depolarization ratios, infrared and Raman absorption vibrational spectra of fullerenols [C(60)(OH)(n)] with different degrees of hydroxylation by using all-electron density-functional-theory (DFT) methods. Stable arrangements of these molecules were found by means of full geometry optimizations using Becke's three-parameter exchange functional with the Lee, Yang, and Parr correlation functional. This DFT level has been combined with the 6-31G(d,p) Gaussian-type basis set, as a compromise between accuracy and capability to treat highly hydroxylated fullerenes, e.g., C(60)(OH)(36). Thus, the molecular properties of fullerenols were systematically analyzed for structures with n=1, 2, 3, 4, 8, 10, 16, 18, 24, 32, and 36. From the electronic structure analysis of these molecules, we have evidenced an important effect related to the weak chemical reactivity of a possible C(60)(OH)(24) isomer. To investigate Raman scattering and the vibrational spectra of the different fullerenols, frequency calculations are carried out within the harmonic approximation. In this case a systematic study is only performed for n=1-4, 8, 10, 16, 18, and 24. Our results give good agreements with the expected changes in the spectral absorptions due to the hydroxylation of fullerenes.

Reconstruction of core and surface nanoparticles: The example of Pt(55) and Au(55)

Cuboctahedron (CUB) and icosahedron (ICO) model structures are widely used in the study of transition-metal (TM) nanoparticles (NPs), however, it might not provide a reliable description for small TM NPs such as the Pt(55) and Au(55) systems in gas phase. In this work, we combined density-functional theory calculations with atomic configurations generated by the basin hopping Monte Carlo algorithm within the empirical Sutton-Chen embedded atom potential. We identified alternative lower energy configurations compared with the ICO and CUB model structures, e. g., our lowest energy structures are 5.22 eV (Pt(55)) and 2.01 eV (Au(55)) lower than ICO. The energy gain is obtained by the Pt and Au diffusion from the ICO core region to the NP surface, which is driven by surface compression (only 12 atoms) on the ICO core region. Therefore, in the lowest energy configurations, the core size reduces from 13 atoms (ICO, CUB) to about 9 atoms while the NP surface increases from 42 atoms (ICO, CUB) to about 46 atoms. The present mechanism can provide an improved atom-level understanding of small TM NPs reconstructions.

Excitation energies from ground-state density-functionals by means of generator coordinates

The generator-coordinate method is a flexible and powerful reformulation of the variational principle. Here we show that by introducing a generator coordinate in the Kohn-Sham equation of density-functional theory, excitation energies can be obtained from ground-state density functionals. As a viability test, the method is applied to ground-state energies and various types of excited-state energies of atoms and ions from the He and the Li isoelectronic series. Results are compared to a variety of alternative DFT-based approaches to excited states, in particular time-dependent density-functional theory with exact and approximate potentials.