Atomic Sphere Approximation Research Articles

Li12Cu12.60Al14.37: a new ternary derivative of the binary Laves phases

New ternary dodecalithium dodecacopper tetradecaaluminium, Li(12)Cu(12.60)Al(14.37) (trigonal, R ̅3m, hR39), crystallizes as a new structure type and belongs to the structural family that derives from binary Laves phases. The Li atoms are enclosed in 15- and 16-vertex and the Al3 atom in 14-vertex pseudo-Frank-Kasper polyhedra. The polyhedra around the statistical mixtures of (Cu,Al)1 and (Al,Cu)2 are distorted icosahedra. The electronic structure was calculated by the TB-LMTO-ASA (tight-binding linear muffin-tin orbital atomic spheres approximation) method. The electron localization function, which indicates bond formation, is mostly located at the Al atoms. Thus, Al-Al bonding is much stronger than Li-Al or Cu-Al bonding. This indicates that, besides metallic bonding which is dominant in this compound, weak covalent Al-Al interactions also exist.

Structural, magnetic and magneto-optical properties of ultrathin films of nickel on iridium (001)

A detailed theoretical study of the structural, magnetic and magneto-optical behaviours of ultrathin films of nickel grown by pseudomorphic epitaxy on semi-infinite Ir(001) is given. The crystalline structure is found to be body centered tetragonal. The total energies are calculated by Spin-Polarized Relativistic Linear Muffin-Tin Orbitals with Atomic Sphere Approximation method. The calculation of the magnetic properties shows a ferromagnetic inter-layer coupling. The polar magneto-optical Kerr effect spectra are calculated over a photon energy range extended to 9 eV. The microscopic origin of the most interesting features is explained by the interband transitions between the localized spin projected states. These transitions are characterized by a spin-flip.

Compton scattering studies and electronic properties of cerium

Experimental electron momentum density of γ-Ce was measured at an intermediate resolution (0.38 a.u.) using 20 Ci 137Cs Compton spectrometer. The experiment was compared with the first ever theoretical Compton profiles computed using spin polarized relativistic Korringa-Kohn-Rostoker (SPR-KKR) method within atomic sphere approximation; and linear combination of atomic orbitals (LCAO) within generalised gradient approximation (GGA) and recently developed second order generalised gradient approximation (SOGGA). It was seen that the Compton profile derived from LCAO with GGA and SOGGA schemes gave a reasonable agreement with the experimental Compton line shape. Theoretical anisotropies in Compton profiles derived along [100], [110] and [111] directions were explained in terms of degenerate states in the energy bands.

Relativistic Effects and Gold Site Distributions: Synthesis, Structure, and Bonding in a Polar Intermetallic Na6Cd16Au7

Na(6)Cd(16)Au(7) has been synthesized via typical high-temperature reactions, and its structure refined by single crystal X-ray diffraction as cubic, Fm ̅3m, a = 13.589(1) Å, Z = 4. The structure consists of Cd(8) tetrahedral star (TS) building blocks that are face capped by six shared gold (Au2) vertexes and further diagonally bridged via Au1 to generate an orthogonal, three-dimensional framework [Cd(8)(Au2)(6/2)(Au1)(4/8)], an ordered ternary derivative of Mn(6)Th(23). Linear muffin-tin-orbital (LMTO)-atomic sphere approximation (ASA) electronic structure calculations indicate that Na(6)Cd(16)Au(7) is metallic and that ∼76% of the total crystal orbital Hamilton populations (-ICOHP) originate from polar Cd-Au bonding with 18% more from fewer Cd-Cd contacts. Na(6)Cd(16)Au(7) (45 valence electron count (vec)) is isotypic with the older electron-richer Mg(6)Cu(16)Si(7) (56 vec) in which the atom types are switched and bonding characteristics among the network elements are altered considerably (Si for Au, Cu for Cd, Mg for Na). The earlier and more electronegative element Au now occupies the Si site, in accord with the larger relativistic bonding contributions from polar Cd-Au versus Cu-Si bonds with the neighboring Cd in the former Cu positions. Substantial electronic differences in partial densities-of-states (PDOS) and COHP data for all atoms emphasize these. Strong contributions of nearby Au 5d(10) to bonding states without altering the formal vec are the likely origin of these effects.

First-principles study of electronic structure of transition metal nitride: ReN under normal and high pressure

First-principles calculation was performed using tight-binding LMTO method with local density approximation (LDA) and atomic sphere approximation (ASA) to understand the electronic properties of rhenium nitride. The equilibrium geometries, the electronic band structure, the total and partial DOS are obtained under various pressures and are analyzed in comparison with the available experimental data. The most stable structure of ReN is NiAs like structure. Our results indicate that ReN can be used as a super-hard conductor. We estimated the average electron–phonon coupling constant to be 1.65 and superconducting transition temperature ( T c) is 5.1 K. The T c value increases with the increase in pressure.

First principles study of pressure-induced magnetic transition in CrN

First principles calculation was performed using tight-binding LMTO method with local density approximation (LDA) and atomic sphere approximation (ASA) to understand the electronic properties of chromium nitride. The equilibrium geometries, the magnetic moment, the electronic band structure, the total and partial DOS are obtained under various pressures and are analyzed in comparison with the available experimental data. The most stable structure of CrN is NaCl structure in the FM state. A pressure-induced second order magnetic phase transition from ferromagnetic (FM) to non-magnetic (NM) at very high pressure of 0.5549Mbar is predicted. Our results indicate that CrN can be used as a hydrogen storage material.

Complete Titanium Substitution by Boron in a Tetragonal Prism: Exploring the Complex Boride Series Ti3−xRu5−yIryB2+x (0 ≤ x ≤ 1 and 1 < y < 3) by Experiment and Theory

Polycrystalline samples and single crystals of four members of the new complex boride series Ti(3-x)Ru(5-y)Ir(y)B(2+x) (0 ≤ x ≤ 1 and 1 < y < 3) were synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. The new silvery phases were structurally characterized by powder and single-crystal X-ray diffraction as well as energy- and wavelength-dispersive X-ray spectroscopy analyses. They crystallize with the tetragonal Ti(3)Co(5)B(2) structure type in space group P4/mbm (No. 127). Tetragonal prisms of Ru/Ir atoms are filled with titanium in the boron-poorest phase (Ti(3)Ru(2.9)Ir(2.1)B(2)). Gradual substitution of titanium by boron then results in the successive filling of this site by a Ti/B mixture en route to the complete boron occupation, leading to the boron-richest phase (Ti(2)Ru(2.8)Ir(2.2)B(3)). Furthermore, both ruthenium and iridium share two sites in these structures, but a clear Ru/Ir site preference is found. First-principles density functional theory calculations (Vienna ab initio simulation package) on appropriate structural models (using a supercell approach) have provided more evidence on the stability of the boron-richest and -poorest phases, and the calculated lattice parameters corroborate very well with the experimentally found ones. Linear muffin-tin orbital atomic sphere approximation calculations further supported these findings through crystal orbital Hamilton population bonding analyses, which also show that the Ru/Ir-B and Ru/Ir-Ti heteroatomic interactions are mainly responsible for the structural stability of these compounds. Furthermore, some stable and unstable phases of this complex series could be predicted using the rigid-band model. According to the density of states analyses, all phases should be metallic conductors, as was expected from these metal-rich borides.

Roles of the band filling and the d orbitals hybridization on the conduction and magnetism of some Sr-based double perovskites: An LSDA+ U study

We have systematically investigated the electronic structure and magnetic properties of the double perovskite oxides Sr 2CrZrO 6, Sr 2MnNbO 6, Sr 2FeMoO 6 and Sr 2NiRuO 6 in terms of band filling of different t 2g and e g orbitals. Calculations of density of the states (DOS) were performed within the frame of the local spin density approximation and Hubbard potential (LSDA+ U) employed in the Linear Muffin Tin Orbitals with Atomic Sphere Approximation (LMTO-ASA) method. The DOS of Sr 2FeMoO 6 was obtained and found to agree very well with published reports. Half-metallic character through the spin-down channel and the ferrimagnetic ordering was observed with notable hybridization among the 3d, p and 4d orbitals within Fermi level. A difference between the theoretically expected values and the calculated ones for the magnetic moment (Δ m) of the 3d orbitals is determined and had been found to increase on going from Sr 2CrZrO 6 to Sr 2NiRuO 6. This increment in Δ m indicates increment in the hybridization strength, which leads to long range ordering in Sr 2FeMoO 6 and Sr 2NiRuO 6 compounds. In comparison with reported experiments, the frustrated magnetism and weak ferrimagnetism states are the most possible ones in Sr 2CrZrO 6 in Sr 2MnNbO 6, respectively. The half-metallic character was also seen in Sr 2MnNbO 6 and Sr 2CrZrO 6 compounds while Sr 2NiRuO 6 shows normal metallic conduction and ferromagnetism in accordance with the superexchange interaction e g 2–o–e g 0 of Goodenough–Kanamori–Anderson (GKA).

Physical properties of GdFe2(AlxZn1−x)20

The high ferromagnetic ordering temperature of the dilute, rare-earth-bearing, intermetallic compound ${\mathrm{GdFe}}_{2}{\mathrm{Zn}}_{20}$ has been understood as being the consequence of the Gd${}^{3+}$ moment being embedded in a nearly ferromagnetic Fermi liquid. To test this understanding in detail, single crystals of the pseudoternary series ${\mathrm{GdFe}}_{2}({\mathrm{Al}}_{x}{\mathrm{Zn}}_{1\ensuremath{-}x}{)}_{20}$ ($x\ensuremath{\leqslant}0.122$) and ${\mathrm{YFe}}_{2}({\mathrm{Al}}_{x}{\mathrm{Zn}}_{1\ensuremath{-}x}{)}_{20}$ ($x\ensuremath{\leqslant}0.121$) were grown out of Zn-rich solution. Magnetization, heat capacity, and resistivity measurements show that, with Al doping, the ferromagnetic phase transition temperatures of the ${\mathrm{GdFe}}_{2}({\mathrm{Al}}_{x}{\mathrm{Zn}}_{1\ensuremath{-}x}{)}_{20}$ compounds decrease from 86 K ($x=$ 0) to 10 K ($x=$ 0.122); for the nonmagnetic analog, the ${\mathrm{YFe}}_{2}({\mathrm{Al}}_{x}{\mathrm{Zn}}_{1\ensuremath{-}x}{)}_{20}$ series, the Stoner enhancement factor $Z$ decreases from 0.88 ($x=$ 0) to 0.35 ($x=$ 0.121) in a similar manner. Tight-binding linear-muffin-tin orbital atomic-sphere approximation band structure calculations are used to rationalize this trend. These results, together with the earlier studies of the $R({\mathrm{Fe}}_{1\ensuremath{-}x}{\mathrm{Co}}_{x}{)}_{2}{\mathrm{Zn}}_{20}$ ($R=$ Gd and Y) series, clearly highlight the importance of band filling and the applicability of even a simple, rigid-band model to these compounds.

Anisotropy analysis of surface energy and prediction of surface segregation for fcc metals

In the atomic scale, the surface energy anisotropy analysis of 38 surface planes of 10 fcc metals Cu, Ag, Au, Ni, Pd, Pt, Rh, Al, Ir and Pb have been simulated by using the elemental variables φ* and nWS and modified analytical embedded-atom method (MAEAM). The results show that the close-packed surface (111) of fcc metals which have the lowest surface energies will grow preferentially, the surface energies for all the other surface planes increase linearly with cosθ(hkl), where cosθ(hkl) are the angles between the surface planes (hkl) and (111), which is consistent with the experimental and the linear-muffin-tin-orbital atomic-sphere approximation (LMTO－ASA) results. A graphical approach which correctly explains the relation of the surface segregation energy and surface energy is employed. We conclude that the surface segregation takes place or not is mainly determined by the rule that an impurity (solute) with lower surface energy will segregate to the surface of the host (solution) with higher surface energy.

Electronic Structure of Heavy-Fermion Systems YbT2Zn20(T= Fe, Co, Ru, Rh, Os, Ir)

Electronic band structure calculations were carried out for dilute rare earth bearing family of R T 2 Zn 20 ( R = Y, Yb, Lu, T = Fe, Co, Ru, Rh, Os, Ir) adopting the linear muffin-tin-orbital method in the atomic sphere approximation within the framework of the local spin-density approximation (LSDA). The Fermi energies in the 4f-itinerant band structures are found to be located in the immediate vicinity of the 4f-band of the j = 7/2 state with extremely narrow band width. In the Yb A 2 Zn 20 ( A = Fe, Ru, and Os) compounds, the j = 7/2 bands are situated just below the Fermi level. In the Yb B 2 Zn 20 ( B = Co, Rh, and Ir) compounds, the j = 7/2 bands touch the Fermi level. These trends of the 4f-bands are consistent with thermodynamic and transport properties. The calculated de Haas–van Alphen (dHvA) frequencies fairly well reproduce the data detected in pulsed fields directed along [110] and [111] directions for Yb X 2 Zn 20 ( X = Fe, Co, and Rh), Lu X 2 Zn 20 ( X = Fe and Co), and YCo 2 Zn 20 , althou...

First-principles theoretical studies of half-metallic ferromagnetism in CrTe

Using full-potential linear augmented plane-wave method (FP-LAPW) we have studied the stability and electronic properties of the chalcogenide CrTe in three competing structures: rocksalt (RS), zinc blende (ZB), and the NiAs-type (NA) hexagonal. Although the ground state is of NA structure, RS and ZB are interesting in that these fcc-based structures, which can perhaps be grown on various semiconductor substrates, exhibit half-metallic (HM) phases above some critical values of the lattice parameter. We find that the NA structure is not HM at its equilibrium volume while both ZB and RS structures are. The RS structure is more stable than the ZB with an energy that is lower by 0.25 eV/atom. While confirming previous results on the HM phase in ZB structure, we provide hitherto unreported results on the HM RS phase, with a gap in the minority channel and a magnetic moment of $4.0\text{ }{\ensuremath{\mu}}_{B}/\text{f}\text{.u}\text{.}$ A comparison of total energies for the ferromagnetic (FM), nonmagnetic, and antiferromagnetic (AFM) configurations shows the lowest energy configuration to be FM for CrTe in all the three structures. The exchange interactions in the RS and ZB structures are studied for a wide range of the lattice parameter using the linear-response method and a mapping of the total energy to the classical Heisenberg model. These linear-response calculations are performed in the linear muffin-tin orbitals (LMTOs) basis, using the atomic sphere approximation (ASA). We have verified that the results of the electronic structure obtained via the LMTO-ASA method under local-density approximation (LDA) and $\text{LDA}+U$ schemes are in close agreement with those obtained via the more accurate FP-LAPW method. The results show that the exchange interactions in the RS structure are much more short ranged than in the ZB structure. Hence, for the RS structure the exchange interactions are also studied by using a nearest- and next-nearest-neighbor $({J}_{1}\text{\ensuremath{-}}{J}_{2})$ model and the energy differences between FM and two AFM states. These ${J}_{1}\text{\ensuremath{-}}{J}_{2}$ model results are obtained by using both the FP-LAPW and LMTO-ASA methods and compared with the linear-response results. The calculated Curie temperatures for the RS phase are consistently higher than those for the ZB phase.

Effect of mono vacancy on electron and positron properties of 3C SiC

AbstractFirst principle calculation of the electron and positron band structure in the perfect and defected 3C silicon carbide (SiC) is performed within the linear muffin‐tin orbital (LMTO) method in the atomic spheres approximation (ASA). For Si and C vacancy the insulator‐metal transition is observed. Effect of the electron–positron interaction on the resulting positron distribution is studied. Theoretical electron and electron–positron momentum densities for Si and C mono vacancies, obtained within various approximations to the electron–positron correlations, are discussed in comparison with the relevant characteristics in the perfect 3C SiC.

The Role of Stereoactive Lone Pairs in Templated Vanadium Tellurite Charge Density Matching

The role of charge density matching was investigated in the formation of templated vanadium tellurites under mild hydrothermal conditions. Reactions were conducted using a fixed NaVTeO(5):amine ratio in an ethanol/water solution to isolate the effects of amine structure. The use of 1,4-diaminobutane, 1,3-diaminopropane, and piperazine resulted in three distinct vanadium tellurite connectivities, [V(2)Te(2)O(10)](n)(2n-) chains, [V(2)TeO(8)](n)(2n-) layers, and [V(2)Te(2)O(10)](n)(2n-) layers, respectively. Charge density matching with the protonated amines is the primary influence over the structure of each vanadium tellurite anion, as quantified by molecular surface area and geometric decomposition methods. Electron localization functions were calculated using the Stuttgart tight-binding linear muffin-tin orbital, atomic sphere approximation code, to visualize the location and relative size, shape, and orientation of the stereoactive lone pair in the tellurite groups. [C(4)H(14)N(2)][V(2)Te(2)O(10)]: a = 5.649(5) A, b = 6.348(5) A, c = 9.661(5) A, alpha = 84.860(5) degrees , beta = 85.380(5) degrees , gamma = 81.285(5) degrees , triclinic, P1 (No. 2), Z = 1.

On the Structural Chemistry of γ‐Brasses: Two Different Interpenetrating Networks in Ternary F‐Cell Pd–Zn–Al Phases

Novel ternary phases, (Pd(1-x)Zn(x))(18)(Zn(1-y)Al(y))(86-delta) (0<or=x<or=0.162, 0.056</=y<or=0.088, 0<or=delta<or=4), which adopt a superstructure of the gamma-brass type (called gamma'-brass), have been synthesized from the elements at 1120 K. Single-crystal X-ray structural analysis reveals a phase width (F43m, a=18.0700(3)-18.1600(2) A, Pearson symbols cF400-cF416), which is associated with structural disorder based on both vacancies as well as mixed site occupancies. These structures are constructed of four independent 26-atom gamma-clusters per primitive unit cells and centered at the four special positions A (0, 0, 0), B (1/4, 1/4, 1/4), C (1/2, 1/2, 1/2) and D (3/4, 3/4, 3/4). Two of these, centered at B and C, are completely ordered Pd(4)Zn(22) clusters, whereas the other two, centered at A and D, contain all structural disorder in the system. According to our single-crystal X-ray results, Al substitutions are restricted to the A- and D-centered clusters. Moreover, the outer tetrahedron (OT) site of the 26-atom cluster at D is completely vacant at the Al-rich boundary of these phases. Electronic structure calculations, using the tight-binding linear muffin-tin orbital atomic-spheres approximation (TB-LMTO-ASA) method, on models of these new, ternary gamma'-brass phases indicate that the observed chemical compositions and atomic distributions lead to the presence of a pseudogap at the Fermi level in the electronic density of states curves, which is consistent with the Hume-Rothery interpretation of gamma-brasses, in general.

Structure and magnetism of pseudobinary L1 alloy FePtM(M=Ir,Au)

We performed energy-band calculations for the L10 pseudobinary bulk alloy FePt1−xMx(M=Ir,Au) by using the linear muffin-tin orbital method with atomic sphere approximations. The exchange-correlation potential was treated within the generalized gradient approximation. The total energies for the ferromagnetic (FM) and three kinds of antiferromagnetic (AFM) states were estimated as a function of lattice ratio c/a∗. For 5d atom substitution, we adopted a virtual crystal approximation. On the basis of the minimum of the total energy, we present the following result: a change in magnetic state (FM-AFM) occurs around FePt1−xMx. It is pointed out that the magnetic state change also depends on the number of valence electrons.

Structural and Magnetic Characteristics of Gd5GaxSi4−x

A crystallographic study and theoretical analysis of the Si/Ga site preferences in the Gd(5)Ga(x)Si(4-x) series is presented. Gd(5)Ga(x)Si(4-x) adopt the orthorhombic Gd(5)Si(4)-type structure (space group Pnma, Z = 4) with a maximum Ga content near x = 1.00, as determined by single crystal and powder X-ray diffraction. Refinements from single crystal X-ray diffraction studies of the three independent sites for Si/Ga atoms in the asymmetric unit (interslab T1, intraslab T2 and T3) reveal partial mixing of these elements, with a clear preference for Ga substitution at the interslab T1 sites. To investigate site preferences of Si/Ga atoms, first-principles electronic structure calculations were carried out using the Vienna ab initio simulation package (VASP) and the Stuttgart tight-binding, linear-muffin-tin orbital program with the atomic sphere approximation (TB-LMTO-ASA). Analysis of various crystal orbital Hamilton population (COHP) curves provide some further insights into the structural tendencies and indicate the roles of both sizes and electronegativities of Ga and Si toward influencing the observed upper limit in Ga content in Gd(5)Ga(x)Si(4-x). The magnetic properties of two Gd(5)Ga(x)Si(4-x) phases are also reported: both show ferromagnetic behavior with Curie temperatures lower than that for Gd(5)Si(4).

Comment on “Doping Driven (π, 0) Nesting and Magnetic Properties ofFe1+xTeSuperconductors”

In this Comment, using Korringa-Kohn-Rostoker coherent-potential approximation method in the atomic-sphere approximation (KKR-ASA CPA) to describe the effects of disorder due to excess Fe in FeTe alloys, we show that (i) the rigid-band approximation is inadequate to describe the effects of disorder and its application leads to an incorrect description of the underlying physics, (ii) the rigid-band energy shift of ~0.76 eV for going from FeTe to Fe_{1.068}Te (or Fe_{1.063}Te), as obtained by Han and Savrasov (Phys. Rev. Lett. 103, 067001(2009)), is inconsistent with our FP-LMTO as well as the KKR-ASA results, and thus the FS of Fe_{1.063}Te shown in Fig. 3(b) of their paper is not correct.

Exchange interactions and Curie temperatures in Cr-based alloys in the zinc blende structure: Volume- and composition-dependence from first-principles calculations

We present calculations of the exchange interactions and Curie temperatures in Cr-based pnictides and chalcogenides of the form $\text{Cr}X$, with $X=\text{As}$, Sb, S, Se, and Te, and the mixed alloys ${\text{CrAs}}_{50}{X}_{50}$, with $X=\text{Sb}$, S, Se, and Te. The calculations are performed for zinc blende structure for 12 values of the lattice parameter between 5.44 and $6.62\text{ }\text{\AA{}}$, appropriate for some typical II-VI and III-V semiconducting substrates. Electronic structure is calculated via the linear muffin-tin-orbitals (LMTOs) method in the atomic sphere approximation (ASA) using empty spheres to optimize ASA-related errors. Whenever necessary, the results have been verified using the full-potential version of the method, FP-LMTO. The disorder effect in the As-sublattice for ${\text{CrAs}}_{50}{X}_{50}$ $(X=\text{Sb},\text{S},\text{Se},\text{Te})$ alloys is taken into account via the coherent-potential approximation. Exchange interactions are calculated using the linear-response method for the ferromagnetic (FM) reference states of the alloys as well as the disordered local moments (DLM) states. These results are then used to estimate the Curie temperature from the low- and high-temperature sides of the ferromagnetic-paramagnetic transition. Estimates of the Curie temperature are provided based on the mean field and the more accurate random-phase approximations. Dominant antiferromagnetic exchange interactions for some low values of the lattice parameter for the FM reference states in CrS, CrSe, and CrTe prompted us to look for antiferromagnetic (AFM) configurations for these systems with energies lower than the corresponding FM and DLM values. Results for a limited number of such AFM calculations are discussed, identifying the AFM[111] state as a likely candidate for the ground state for these cases.

Structural and electronic properties of Er-monopnictides under high pressure

Abstract We present the results of theoretical calculations on the structural, magnetic and electronic properties of Er-monopnictides using self-consistent first principles tight-binding linear-muffin-tin-orbital (TB-LMTO) method within the atomic-sphere approximation (ASA). Both spin-polarized and non-spin-polarized calculations are performed to check the magnetic stability of these compounds. We find that ErN, ErP and ErAs are metallic in ferromagnetic (FM) phase in both the spin channels and stable in NaCl-type (B1) structure at ambient pressure. We predict NaCl-type (B1) to CsCl-type (B2) structural phase transition in ErN, ErP and ErAs at pressures of 146.1, 60.2 and 53.2 GPa, respectively and remain metallic ferromagnetic at high pressure. We calculate equilibrium lattice constants (a), bulk modulus (B), magnetic moments (μB) and electronic properties of these compounds in B1 and B2 phases and compare with available experimental and theoretical results.