Ab Initio Density-functional Theory Calculations Research Articles

Four allotropes of semiconducting layered arsenic that switch into a topological insulator via an electric field: Computational study

We propose four different thermodynamically stable structural phases of arsenic monolayers based on ab-initio density functional theory calculations all of which undergo a topological phase transition on application of a perpendicular electric field. All the four arsenic monolayer allotropes have a wide band gap, varying from 1.21 eV to 3.0 eV (based on GW calculations), and in general they undergo a metal-insulator quantum phase transition on application of uniaxial in-layer strain. Additionally an increasing transverse electric field induces band-inversion at the {\Gamma} point in all four monolayer allotropes, leading to a nontrivial topological phase (insulating for three and metallic for one allotrope), characterized by the switching of the Z2 index, from 0 (before band inversion) to 1 (after band inversion). The topological phase tuned by the transverse electric field, should support spin-separated gapless edge states which should manifest in quantum spin Hall effect.

Magnetoelectroelastic control of magnetism in an artificial multiferroic

We study the coexistence of strain- and charge-mediated magnetoelectric coupling in a cobalt (0-7 nm) wedge on ferroelectric [Pb(Mg$_{1/3}$/Nb$_{2/3}$)O$_{3}$]$_{0.68}$-[PbTiO$_{3}$]$_{0.32}$ (011) using surface-sensitive x-ray magnetic circular dichroism spectroscopy at the Co L$_{3,2}$ edges. Three distinct electric field driven remanent magnetization states can be set in the Co film at room temperature. Ab-initio density functional theory calculations unravel the relative contributions of both strain and charge to the observed magnetic anisotropy changes illustrating magnetoelectro-elastic coupling at artificial multiferroic interfaces.

Thermodynamics and Kinetics of Li Extraction from Li-Rich Layered Manganese Oxide Cathodes

Li-rich layered oxides Li1+xM1-xO2 (0<x<0.33), where M=Co, Mn, Ni, have emerged as promising cathode materials, because they can deliver much higher capacities (> 250 mAh/g) than the conventional LiCoO2 cathode. Important issues relate to what is the origin of the electrochemical activity and high capacity? In this work, possible charge compensation mechanisms upon lithium extraction from Li2MnO3 are studied by ab-initio density functional theory calculations: (a) Reversible oxidation of bulk O2- to other anion species such as superoxide or peroxide; (b) Loss of lattice oxygen (oxygen evolution). Both thermodynamic (reaction enthalpies and electrochemical potentials) and kinetic (ion migration) aspects are investigated.

Prospect of quantum anomalous Hall and quantum spin Hall effect in doped kagome lattice Mott insulators.

Electronic states with non-trivial topology host a number of novel phenomena with potential for revolutionizing information technology. The quantum anomalous Hall effect provides spin-polarized dissipation-free transport of electrons, while the quantum spin Hall effect in combination with superconductivity has been proposed as the basis for realizing decoherence-free quantum computing. We introduce a new strategy for realizing these effects, namely by hole and electron doping kagome lattice Mott insulators through, for instance, chemical substitution. As an example, we apply this new approach to the natural mineral herbertsmithite. We prove the feasibility of the proposed modifications by performing ab-initio density functional theory calculations and demonstrate the occurrence of the predicted effects using realistic models. Our results herald a new family of quantum anomalous Hall and quantum spin Hall insulators at affordable energy/temperature scales based on kagome lattices of transition metal ions.

Quasi-particle energies and optical excitations of wurtzite BeO and its nanosheet

The electronic and optical properties of BeO in wurtzite bulk and sheet structures are investigated by using ab-initio density functional theory calculations combined with many-body perturbation formalism. The electronic properties were analyzed at three levels of the many-body GW approach (G0W0, GW0 and GW) constructed over a Generalized Gradient Approximation functional. Our results show that GW approach does not change the sort of direct or indirect band gap in bulk or sheet systems of BeO. The best result for the insulating gap of the bulk system was obtained at the GW0 level. The optical properties and excitonic effects of these materials are investigated using the Bethe-Salpeter equation (BSE) approach. Comparison with experiment shows that the optical properties of the bulk system cannot be explained by independent-particle transitions but they are strongly dominated by excitonic effects. The binding energies of the first exciton for the bulk and sheet structures are 0.5 and 1.5 eV in E||x, respectively. The quantum confinement of BeO sheet significantly enhances the electron-hole interaction and finally leads to a larger binding energy. We show that the spectrum for both bulk and sheet systems is dominated by strongly bound Frenkel excitons.

Quantum hydrogen-bond symmetrization in the superconducting hydrogen sulfide system.

The quantum nature of the proton can crucially affect the structural and physical properties of hydrogen compounds. For example, in the high-pressure phases of H2O, quantum proton fluctuations lead to symmetrization of the hydrogen bond and reduce the boundary between asymmetric and symmetric structures in the phase diagram by 30 gigapascals (ref. 3). Here we show that an analogous quantum symmetrization occurs in the recently discovered sulfur hydride superconductor with a superconducting transition temperature Tc of 203 kelvin at 155 gigapascals--the highest Tc reported for any superconductor so far. Superconductivity occurs via the formation of a compound with chemical formula H3S (sulfur trihydride) with sulfur atoms arranged on a body-centred cubic lattice. If the hydrogen atoms are treated as classical particles, then for pressures greater than about 175 gigapascals they are predicted to sit exactly halfway between two sulfur atoms in a structure with Im3m symmetry. At lower pressures, the hydrogen atoms move to an off-centre position, forming a short H-S covalent bond and a longer H···S hydrogen bond in a structure with R3m symmetry. X-ray diffraction experiments confirm the H3S stoichiometry and the sulfur lattice sites, but were unable to discriminate between the two phases. Ab initio density-functional-theory calculations show that quantum nuclear motion lowers the symmetrization pressure by 72 gigapascals for H3S and by 60 gigapascals for D3S. Consequently, we predict that the Im3m phase dominates the pressure range within which the high Tc was measured. The observed pressure dependence of Tc is accurately reproduced in our calculations for the phase, but not for the R3m phase. Therefore, the quantum nature of the proton fundamentally changes the superconducting phase diagram of H3S.

Electronic Structure Evolution during the Growth of Graphene Nanoribbons on Au(110)

Surface-assisted polymerization of molecular monomers into extended chains can be used as the seed of graphene nanoribbon (GNR) formation, resulting from a subsequent cyclo-dehydrogenation process. By means of valence-band photoemission and ab-initio density-functional theory (DFT) calculations, we investigate the evolution of molecular states from monomer 10,10'-dibromo-9,9'bianthracene (DBBA) precursors to polyanthryl polymers, and eventually to GNRs, as driven by the Au(110) surface. The molecular orbitals and the energy level alignment at the metal-organic interface are studied in depth for the DBBA precursors deposited at room temperature. On this basis, we can identify a spectral fingerprint of C-Au interaction in both DBBA single-layer and polymerized chains obtained upon heating. Furthermore, DFT calculations help us evidencing that GNRs interact more strongly than DBBA and polyanthryl with the Au(110) substrate, as a result of their flatter conformation.

The role of silicon, vacancies, and strain in carbon distribution in low temperature bainite

We investigated the phenomenon of carbon supersaturation and carbon clustering in bainitic ferrite with atom probe tomography (APT) and ab-initio density functional theory (DFT) calculations. The experimental results show a homogeneous distribution of silicon in the microstructure, which contains both ferrite and retained austenite. This distribution is mimicked well by the computational approach. In addition, an accumulation of C in certain regions of the bainitic ferrite with C concentrations up to 13 at % is observed. Based on the DFT results, these clusters are explained as strained, tetragonal regions in the ferritic bainite, in which the solution enthalpy of C can reach large, negative values. It seems that Si itself only has a minor influence on this phenomenon.

A large-scale simulation method on complex ternary Li–Mn–O compounds for Li-ion battery cathode materials

To meet the requirement of large-scale simulation technics for Li-ion battery electrode materials, we introduce the charge-transfer modified embedded-atom method (CT-MEAM) in which the complex nature of the chemical bonding in transition metal (TM) oxides is described as a balance between metallic/covalent and ionic contributions by MEAM and a variable-charge model, respectively. The method is applied to Li2MnO3, and the parameterization is performed through fitting the energy–strain curves of Li2MnO3 under uniaxial, biaxial and hydrostatic strains to a training set from ab initio density-functional theory calculations. The CT-MEAM prediction of the critical physical properties such as charge states and redox potentials match quite well with the ab initio results in various Li–Mn–O compounds beyond Li2MnO3. The constructed Li–Mn–O phase diagram is also qualitatively consistent with the ab initio reference work. The excellent transferability ensures use of the present method for a wide range of oxidation states in complex ternary TM oxides. Therefore, it will facilitate large-scale atomistic calculations required for the optimal design of many TM oxide applications including lithium-ion battery cathode materials.

Electronic and magnetic properties ofGaFeO3:Ab initiocalculations for varying Fe/Ga ratio, inner cationic site disorder, and epitaxial strain

In this study we present ab initio density-functional theory calculations on stoichiometric, cation-doped, and strained $\mathrm{GaFeO}{}_{3}$. We start with a detailed discussion of the origin of the antiferromagnetic (AFM) superexchange in stoichiometric $\mathrm{GaFeO}{}_{3}$ and give a molecular orbital description of the exchange mechanism derived from our calculations. In addition, we study the properties of the Fe-O-Fe bonds for different geometries to underline the angle and distance dependence of the AFM coupling as formulated in the Goodenough-Kanamori rules. We describe the AFM ground state of $\mathrm{GaFeO}{}_{3}$ as a result of two intrinsic Fe-O-Fe chains that meander through the crystal along the $c$ direction. The magnetocrystalline anisotropy energies are calculated for the stoichiometric phase with and without inner cationic site disorder, and the presence of a sublattice-dependent anisotropy is examined. Furthermore, we perform our studies of ${\mathrm{Ga}}_{2\ensuremath{-}x}\mathrm{Fe}{}_{x}{\mathrm{O}}_{3}$ for varying Fe concentrations $\mathit{x}(0.0\ensuremath{\le}\mathit{x}\ensuremath{\le}2.0)$ where at a value of $\mathit{x}=0.0$ and $\mathit{x}=2.0$ it transforms into the isomorphic $\ensuremath{\varepsilon}\text{\ensuremath{-}}\mathrm{Ga}{}_{2}{\mathrm{O}}_{3}$ and $\ensuremath{\varepsilon}\text{\ensuremath{-}}\mathrm{Fe}{}_{2}{\mathrm{O}}_{3}$ phases, respectively. The effect of strain was also studied. Incorporating dopants and applying strain to the simulation cell changes the intrinsic geometry and thus the magnetic properties of gallium ferrite.

THERMAL DIFFUSION DYNAMIC BEHAVIOR OF TWO-DIMENSIONAL Ag-SMALL CLUSTERS ON Ag(1 1 1) SURFACE

In this paper, the thermal diffusion behavior of small two-dimensional Ag -islands on Ag (1 1 1) surface has been explored using molecular dynamics (MD) simulations. The approach is based on semi-empirical potentials. The key microscopic processes responsible for the diffusion of Ag 1−5 adislands on Ag (1 1 1) surface are identified. The hopping and zigzag concerted motion along with rotation are observed for Ag one-atom to three-atom islands while single-atom and multi-atom processes are revealed for Ag four-atom and five-atom islands, during the diffusion on Ag (1 1 1) surface. The same increasing/decreasing trend in the diffusion coefficient and effective energy barrier is observed in both the self learning kinetic Monte Carlo (SLKMC) and MD calculations, for the temperature range of 300–700 K. An increase in the value of effective energy barrier is noticed with corresponding increase in the number of atoms in Ag -adislands. A reasonable linear fit is observed for the diffusion coefficient for studied temperatures (300, 500 and 700 K). For the observed diffusion mechanisms, our findings are in good agreement with ab initio density-functional theory (DFT) calculations for Al / Al (1 1 1) while the energy barrier values are in same range as the experimental values for Cu / Ag (1 1 1) and the theoretical values using ab initio DFT supplemented with embedded-atom method for Ag / Ag (1 1 1).

FT-IR, FT-Raman, UV/Vis spectra and fluorescence imaging studies on 2-(bromoacetyl)benzo(b)furan by ab initio DFT calculations

The vibrational and electronic properties of 2-(bromoacetyl)benzo(b)furan have been studied in the ground state using experimental techniques (FT-IR, FT-Raman and UV) and density functional theory (DFT) employing B3LYP exchange correlation with the 6-31G(d,p) basis set. The theoretically calculated optimized parameters, vibrational frequencies etc., were compared with the experimental values, which yield good agreement between the observed and calculated values. The complete assignments of fundamental modes were performed on the basis of the potential energy distribution (PED). UV–visible spectrum of the compound was recorded in the region 300–600nm and compared with the theoretical spectrum obtained from SAC–CI calculations. A good agreement is observed between the experimental and theoretical spectra. Fluorescence microscopic imaging studies proved that the compound can be used as one of the potential light sources in the yellow region with suitable excitation. Further, the predicted electronic transitions between the MOs 47→64, 52→62, 56→65, 56→72, 56→77 of the compound show a strong line at 569.8nm.

Structural formation of binary PtCu clusters: A density functional theory investigation

Binary transition-metal clusters have attracted great attention and a large number of studies have been reported, however, our atomistic understanding of the structural formation mechanisms of those clusters is still far from satisfactory. In this paper, we report a systematic study of the PtnCum−n clusters (m=2,3,…,14,n=0,1,…,m) employing Ab-Initio density functional theory calculations within the Perdew–Burke–Ernzerhof functional. Using a set of structural design principles, we obtained a hierarchical set of atomic configurations from which the structural formation mechanisms are discussed in details. We found a negative excess energy for m>2, providing strong evidence favouring the formation of binary PtCu clusters. In general, the Cu atoms tend to form agglomerates located near the center of gravity of the clusters while the Pt atoms tend to lie further away from the center of gravity and separated from each other. Therefore, this behaviour tends to reduce the number of Pt–Pt bonds whereas the number of Cu–Cu and Pt–Cu bonds tends to be maximized. These mechanisms help to release strain energy by means of relaxation of the gas-phase clusters, and the locations of the Cu and Pt atoms suggest that the formation of core–shell like structures starts already in this small size regime. Furthermore, the formation of the PtCu alloy does not lead to changes in the magnetic properties of the clusters in comparison with the parent Pt and Cu clusters. The systematic work presented here provides a basis to understand and tailor the properties of binary cluster.

Identifying the role of terahertz vibrations in metal-organic frameworks: from gate-opening phenomenon to shear-driven structural destabilization.

We present an unambiguous identification of low-frequency terahertz vibrations in the archetypal imidazole-based metal-organic framework (MOF) materials: ZIF-4, ZIF-7, and ZIF-8, all of which adopt a zeolite-like nanoporous structure. Using inelastic neutron scattering and synchrotron radiation far-infrared absorption spectroscopy, in conjunction with density functional theory (DFT), we have pinpointed all major sources of vibrational modes. Abinitio DFT calculations revealed the complex nature of the collective THz modes, which enable us to establish detailed correlations with experiments. We discover that low-energy conformational dynamics offers multiple pathways to elucidate novel physical phenomena observed in MOFs. New evidence demonstrates that THz modes are intrinsically linked, not only to anomalous elasticity underpinning gate-opening and pore-breathing mechanisms, but also to shear-induced phase transitions and the onset of structural instability.

Optical spectrum of bottom-up graphene nanoribbons: towards efficient atom-thick excitonic solar cells

Recently, atomically well-defined cove-shaped graphene nanoribbons have been obtained using bottom-up synthesis. These nanoribbons have an optical gap in the visible range of the spectrum which make them candidates for donor materials in photovoltaic devices. From the atomistic point of view, their electronic and optical properties are not clearly understood. Therefore, in this work we carry out ab-initio density functional theory calculations combine with many-body perturbation formalism to study their electronic and optical properties. Through the comparison with experimental measurements, we show that an accurate description of the nanoribbon's optical properties requires the inclusion of electron-hole correlation effects. The energy, binding energy and the corresponding excitonic transitions involved are analyzed. We found that in contrast to zigzag graphene nanoribbons, the excitonic peaks in the absorption spectrum are a consequence of a group of transitions involving the first and second conduction and valence bands. Finally, we estimate some relevant optical properties that strengthen the potential of these nanoribbons for acting as a donor materials in photovoltaic.

Temperature effects on the energy bandgap and conductivity effective masses of charge carriers in lead telluride from first-principles calculations

We determined the temperature effects on the electronic properties of lead telluride (PbTe) such as the energy bandgap and the effective masses of charge carriers by incorporating the structural changes of the material with temperature using ab-initio density functional theory (DFT) calculations. Though the first-principles DFT calculations are done at absolute zero temperatures, by incorporating the lattice thermal expansion and the distortion of Pb2+ ions from the equilibrium positions, we could determine the stable structural configuration of the PbTe system at different temperatures.

Interface properties in lamellar TiAl microstructures from density functional theory

The deformability and strength of lamellar two-phase (γ and α2) TiAl alloys strongly depends on the mechanical properties of the different interfaces in such microstructures. We carried out ab-initio density functional theory calculations of interface energy and strength for all known interface variants as well as the corresponding single crystal slip/cleavage planes to obtain a comprehensive database of key mechanical quantities. This data collection can be used for meso-scale simulations of deformation and fracture in TiAl. In spite of the different atomic configurations of the lamellar interfaces and the single crystal planes, the calculated values for the tensile strength are in the same range and can be considered as equal in a meso-scale model. Analysis of generalized stacking fault energy surfaces showed that the shear strength is directional dependent, however, the [112¯] direction is an invariant easy gliding direction in all investigated systems. The probability of different dislocation dissociation reactions as part of a shear deformation mechanism are discussed as well.

Ab initio and relativistic DFT study of spin-rotation and NMR shielding constants in XF₆ molecules, X = S, Se, Te, Mo, and W.

We present an analysis of the spin-rotation and absolute shielding constants of XF6 molecules (X = S, Se, Te, Mo, W) based on ab initio coupled cluster and four-component relativistic density-functional theory (DFT) calculations. The results show that the relativistic contributions to the spin-rotation and shielding constants are large both for the heavy elements as well as for the fluorine nuclei. In most cases, incorporating the computed relativistic corrections significantly improves the agreement between our results and the well-established experimental values for the isotropic spin-rotation constants and their anisotropic components. This suggests that also for the other molecules, for which accurate and reliable experimental data are not available, reliable values of spin-rotation and absolute shielding constants were determined combining ab initio and relativistic DFT calculations. For the heavy nuclei, the breakdown of the relationship between the spin-rotation constant and the paramagnetic contribution to the shielding constant, due to relativistic effects, causes a significant error in the total absolute shielding constants.

Electronic structure and ionic diffusion of green battery cathode material: Mg2Mo6S8

Abstract We report ab-initio density functional theory calculations of crystal and electronic structure of Mg 2 Mo 6 S 8 , a candidate material to be used in rechargeable magnesium batteries, by employing hybrid exchange–correlation functionals. We find that Mg 2 Mo 6 S 8 crystalizes in a triclinic geometry and it is a semiconductor with an indirect band gap. Ab-initio molecular dynamics shows that Mg ions present progressive diffusion starting at 200 K with a preferable path through the channel between Mo 6 S 8 blocks along the [010] direction. The intercalation voltage of the system is also determined and the results show that the voltage evaluated by PBE and hybrid functionals likely implies the lower and the upper limit of the experimental value. Lastly, we confirm the dynamical stability of the crystal structure by the calculated phonon dispersion relation.

Nitrogen-containing species in the structure of the synthesized nano-hydroxyapatite

Synthesized by the wet chemical precipitation technique hydroxyapatite powders (HAp) with the sizes of the crystallites of (20-50) nm and 1000 nm were analyzed by different analytical methods. By means of electron paramagnetic resonance (EPR) it is shown that during the synthesis process nitrate anions from the reagents (by-products) could incorporate into the HAp structure. The concentration of the stable NO32- radicals detected after X-ray irradiation of the product at room temperature does not decrease even after annealing up to 400 oC. The relaxation times and EPR parameters of the axially symmetric NO32- paramagnetic centers are measured with high accuracy. Increased sensitivity and resolution of high-frequency EPR (95 GHz) allows to reveal additional paramagnetic centre(s) which origin is discussed. Analyses of electron-nuclear double resonance (ENDOR) spectra from 1H and 31P nuclei and ab-initio density functional theory (DFT) calculations allow suggesting that the paramagnetic centers and nitrate anions as the precursors of NO32- radicals preferably occupy PO43- site in the HAp structure.