D. Nguyen-Manh

Electronic structure, phase stability and elastic moduli of AB transition metal aluminides

Abstract Binding energy curves for the 4d transition metal TM aluminides TMAl with respect to 12 different AB-structure types have been computed using the full-potential linear muffin-tin orbitals (FP-LMTO) method within local-density-functional approximation (LDA). Combining with our previous calculations for the 3d TMAl, we find that the observed ground state structures are predicted correctly for all the AB transition metal aluminides including the low-temperature monoclinic C2/m phase of CuAl. Moreover, the B32 phase is predicted to be the most stable amongst competing metastable phases for CrAl, MoAl, TcAl, whereas for VAl and NbAl the most stable phases are L10 and Ω , respectively. The calculated heats of formation are in good agreement with available experimental data. The critical roles played by the average number of valence electrons per atom and the angular character of the valence orbitals are emphasized in explaining the structural phase stability across the TMAl series. In particular, it is shown that the structural trend going from B2 (bcc-like) → L10 (fcc-like) → B19 (hcp-like) → B2 as a function of electron concentration, can be understood from a band structure energy analysis. The calculated electronic structure for all the stable phases of both the 3d and 4d TMAl demonstrates a correlation between structural stability and the shape of the density of states due to the strong directional bonding between the sp(Al) and d(TM) orbitals. Finally, the elastic moduli have been computed for all observed ground states of TMAl with new results for ScAl and RhAl (in the B2 structure), YAl and ZrAl (in the B33 structure) and for PdAl (in the B20 structure).

Electronic structure and energetics of LaNi5, α-La2Ni10H and β-La2Ni10H14

Abstract The electronic structure and energetics of LaNi 5 , its hydrogen solution (α-La 2 Ni 10 H) and its hydride (β-La 2 Ni 10 H 14 ) were investigated by means of the tight-binding linear muffin-tin orbital method within the atomic sphere approximation (TB-LMTO-ASA). Preferred site occupation of the absorbed hydrogen atoms was investigated in terms of the charge density of the interstitial sites and the total energy, both of which indicate that the 6m site in the P 6/ mmm symmetry is the most preferred. A negative heat of formation of La 2 Ni 10 H 14 was obtained after optimising the kinetic energy of the electrons outside the atomic spheres and the interstitial sphere radii.

Self-interstitial atom defects in bcc transition metals: group-specific trends

We report a high-pressure investigation of the relaxor ferroelectric lead zinc niobate PbZn{sub 1/3}Nb{sub 2/3}O{sub 3} (PZN) up to 46 GPa, which is the highest pressure yet attained in the study of relaxors. The evolution of both Raman and x-ray scattering with pressure gives evidence for important pressure instabilities, which find its expression in three successive phase transitions. The observed pressure-induced suppression of diffuse scattering above 5 GPa is similar to recent reports and supports the hypothesis that this is a general feature in relaxors at high pressures.Stable pairing states of superfluid {sup 3}He in aerogel are examined in the case with a global uniaxial anisotropy which may be created by applying a uniaxial stress to the aerogel. Due to such a global anisotropy, the stability region of an Anderson-Brinkman-Morel (ABM) pairing state becomes wider. In a uniaxially stretched aerogel, the pure polar pairing state with a horizontal line node is predicted to occur, as a three-dimensional superfluid phase, over a measurable width just below the superfluid transition at T{sub c}(P). A possible relevance of the present results to the case with no global anisotropy is also discussed.A series of Ca{sub x}CoO{sub 2} (0.15{<=}x{<=}0.40) materials have been prepared by means of an ion exchange reaction from Na{sub x}CoO{sub 2}. Transmission electron microscopy (TEM) measurements revealed a rich variety of structural phenomena resulting from cation ordering, structural distortion, and twinning. Systematic structural analysis, in combination with the experimental data of Na{sub x}CoO{sub 2} (0.15{<=}x{<=}0.8) and Sr{sub x}CoO{sub 2} (1.5{<=}x{<=}0.4) systems, suggests that there are two common well-defined cation ordered states corresponding, respectively, to the orthorhombic superstructure at around x=1/2 and the 3{sup 1/2}ax3{sup 1/2}a superstructure at around x=1/3 in this kind of system. Multiple ordered states, phase separation, and incommensurate structural modulations commonly appear in the materials with 0.33<x<0.5. The TEM observations also reveal an additional periodic structural distortion with q{sub 2}=a{sup *}/2 in materials for x{<=}0.35. This structural modulation also appears in the remarkable superconducting phase Na{sub 0.33}CoO{sub 2}{center_dot}1.3H{sub 2}O.Electrical resistance, thermoelectric power, dc magnetization, ac susceptibility, and electron spin resonance (ESR) are investigated for the polycrystalline Nd{sub 1-x}Sr{sub 1+x}CoO{sub 4} (x=0.25, 0.33, and 0.60). Powder x-ray diffraction (XRD) confirms that these compounds crystallize in K{sub 2}NiF{sub 4}-type structure with space group I4/mmm. The specimens exhibit ferromagnetic and semiconducting behaviors. With Sr doping, the lattice parameter c increases, the cusp intensity related to spin-glass states weakens, and the ferromagnetic property intensifies. The transport mechanisms in high temperature range obey Arrhenius law and might be understood by small polaron models. The magnetic properties present spin-glass states at {approx}18 K and Griffiths singularity at {approx}210 K.In this work we report on a low-energy electron diffraction (LEED) study of MnO(100) thick films grown on Ag(100) in order to determine their surface geometry. The LEED results indicate a topmost layer rumple of (4.8{+-}2.0)% with the oxygen ions moving towards the vacuum side. These results are in line with other surface structure determinations carried out on the (100) surface of different oxides having rock-salt structure but are in disagreement with MEIS results reported in the literature for the MnO(100) using a MnO single crystal.We report the observation of Co{sup 3+}/Co{sup 4+} short-range charge ordering in 10% Ho-doped SrCoO{sub 3-x} by means of high resolution neutron powder diffraction. The associated one-dimensional commensurate modulation, which can be described with the propagation vector q{sub CO}=(0 0 1/2) with respect to the cubic perovskite cell Pm3m, occurs for compositions close to x=0.20, corresponding to a 1:1 Co{sup 3+}/Co{sup 4+} ratio and extends over clusters of finite size (D{approx}250 A). The bond valence sums for the Co{sup 3+} and Co{sup 4+} sites are +3.07(7) and +3.95(11) (x=0.19), very close to their nominal values +3 and +4. We attribute this astonishing observation to the one-dimensional (1D) character of the associated distortion pattern, whose elastic stabilization is eased with respect to the 3D arrays reported for other charge-ordered perovskite oxides.The compounds RNi{sub 2}Mn (R=Tb, Dy, Ho, and Er) with a MgCu{sub 2}-type structure have been synthesized. The R to transition metal atom ratio is confirmed to be 1:3 using the energy dispersive spectroscopy. The structural and magnetic properties have been investigated by various experimental methods. The x-ray diffraction patterns (XRD) can be well indexed with a cubic Laves cell and space group Fd3m. The refinement results of the XRD patterns show the presence of vacancies in the crystallographic structure. The ordering temperatures T{sub C} have been derived to be 131, 94, 75, and 50 K for R=Tb, Dy, Ho and Er, respectively, which are much higher than those of their corresponding RNi{sub 2} and RMn{sub 2} compounds. A large difference of M-T curves between zero-field-cooling and field-cooling magnetization for all samples at a certain temperature range is observed in a low field, which can be understood in the terms of narrow-domain-wall pinning and a sensitive temperature dependence of coercivity.The structure of liquid CdTe was investigated at pressures up to 23.5 GPa using synchrotron x-ray diffraction. The structure factor, S(Q), and the pair distribution function, g(r), drastically change in two pressure regions, 1.8-3.0 and 7.0-9.0 GPa, accompanied with marked increase in the average coordination number. These findings suggest that there exists at least three stable liquid forms below 23.5 GPa. The pressure interval of the structural change is much smaller compared to other liquids of tetrahedrally bonded materials. Comparing the shapes of S(Q) and g(r) and other structural parameters with the respective data for the reference materials reveals that the lowest- and intermediate-pressure forms have the same local structures as the crystalline counterpart (zinc-blende-like local structure and a NaCl-like local structure), while the highest-pressure form has a different local structure from that in the crystalline form.The charge distributions of slow atomic particles that are singly scattered, multiply scattered, recoiled, and sputtered from metal surfaces are analyzed in terms of both nonadiabatic particle-substrate electron transfer and electron transfer from electronically excited substrates. The results are compared to experimental data for 50 eV Na{sup +} ions scattered from Cu(001), and Al atoms sputtered and recoiled from Al(100). The comparison allows for a quantitative determination of the role of substrate excitations in surface charge exchange. In addition, an analysis of kinetic electron emission (KEE) is carried out using similar low-energy metal projectile-metal substrate systems. Contributions to KEE from various nonadiabatic processes are quantitatively evaluated, including the same process that is responsible for charge formation in single-scattering experiments. The results are compared to experimental KEE data induced by Na{sup +} impinging on Ru(0001). The contributions of nonadiabatic one-electron processes are shown to be small when realistic particle-substrate parameters are used. Many-electron interactions are assumed to play an important role in explaining KEE and, as an illustration, a simplified hot-spot model is outlined.Neutron powder diffraction and transport measurements have been used to investigate the PrBaCo{sub 2}O{sub 5.48} compound between room temperature and 820 K. A structural phase transition, involving a rearrangement of oxygen vacancies, was found at T{sub OD}=776 K. Across the transition the perovskite structure loses its vacancy ordering, and the crystal symmetry changes from orthorhombic Pmmm to tetragonal P4/mmm. The resistivity measurements for temperatures above {approx}350 K yield high values of {rho}, indicating that the compound is rather semiconducting than metallic as usually accepted. A model in terms of thermally activated hole (polaronic) hopping is proposed.Granular films composed of well defined nanometric Co particles embedded in an insulating ZrO{sub 2} matrix were prepared by pulsed laser deposition in a wide range of Co volume concentrations (0.15<x<0.43). High-resolution transmission electron microscopy (TEM) showed very sharp interfaces between the crystalline particles and the amorphous matrix. Narrow particle size distributions were determined from TEM and by fitting the low-field magnetic susceptibility and isothermal magnetization in the paramagnetic regime to a distribution of Langevin functions. The magnetic particle size varies little for Co volume concentrations x<0.32 and increases as the percolation limit is approached. The tunneling magnetoresistance (TMR) was successfully reproduced using the Inoue-Maekawa model. The maximum value of TMR was temperature-independent within 50-300 K, and largely increased at low T, suggesting the occurrence of higher-order tunneling processes. Consequently, the tunneling conductance and TMR in clean granular metals are dominated by the Coulomb gap and the inherent particle size distribution.The five independent elastic moduli of single-crystalline hexagonal boron nitride (h-BN) are determined using inelastic x-ray scattering. At room temperature the elastic moduli are in units of GPa C{sub 11}=811, C{sub 12}=169, C{sub 13}=0, C{sub 33}=27.0, and C{sub 44}=7.7. Our experimental results are compared with predictions of ab initio calculations and previously reported incomplete datasets. These results provide solid background for further theoretical advances and quantitative input to model elasticity in boron nitride (BN) nanotubes.I argue that certain bosonic insulator-superfluid phase transitions as an interaction constant varies are driven by emergent geometric properties of insulating states. I examine the renormalized chemical potential and population of disordered bosons at different energy levels. These quantities define the geometric aspect of an effective low energy Hamiltonian which I employ to investigate various resonating states and quantum phase transitions. In a mean field approximation, I also demonstrate that the quantum phase transitions are in the universality class of a percolation problem.The electronic structure and physical properties of {gamma}-Sn{sub 3}N{sub 4} in the spinel structure are investigated by first-principles calculations. The calculated band structure, electronic bonding, and optical properties are compared with two well-studied spinel nitrides {gamma}-Si{sub 3}N{sub 4} and {gamma}-Ge{sub 3}N{sub 4}. {gamma}-Sn{sub 3}N{sub 4} is a semiconductor with a direct band gap of 1.40 eV and an attractive small electron effective mass of 0.17. Its optical properties are different from that of {gamma}-Si{sub 3}N{sub 4} and {gamma}-Ge{sub 3}N{sub 4} because of the difference in the conduction band minimum. The Sn K, Sn L{sub 3}, Sn M{sub 5}, and N K edges of the x-ray-absorption near-edge structure spectra in {gamma}-Sn{sub 3}N{sub 4} are calculated using a supercell approach and are found to be rich in structures. These spectra are discussed in the context of the electronic structure of the unoccupied conduction band in the presence of the electron core-hole interaction. These calculated spectra can be used for the characterization of this novel compound.The structure of the incommensurate phase of Rb{sub 2}ZnCl{sub 4} has been determined at 194 K (2 K above the lock-in transition) within the soliton regime using satellites up to fifth order. The rather anharmonic modulation functions agree with the expected steplike functions supported by theoretical arguments. In addition, the constancy of the ratio between the amplitudes of the fifth-order and first-order harmonics, a relation predicted by theory, indicate the correctness of the model and imply a value of 0.4 for the soliton density n{sub s}. A symmetry mode analysis shows that the incommensurate structure is consistent with the one of the lock-in phase in the sense that the displacement pattern of every symmetry mode remains unaltered in the transition except for a global change in the amplitudes.X-ray diffraction of SnO{sub 2} (cassiterite) at high pressures and temperatures demonstrates the existence of four phase transitions to 117 GPa. The observed sequence of phases for SnO{sub 2} is rutile-type (P4{sub 2}/mnm){yields}CaCl{sub 2}-type(Pnnm){yields}pyrite-type(Pa3){yields}ZrO{sub 2} orthorhombic phase I (Pbca){yields}cotunnite-type (Pnam). Our observations of the first three phases are generally in agreement with earlier studies. The orthorhombic phase I and cotunnite-type structure (orthorhombic phase II) were observed in SnO{sub 2} for the first time. The Pbca phase is found at 50-74 GPa during room-temperature compression. The cotunnite-type structure was synthesized when SnO{sub 2} was compressed to 74 GPa and heated at 1200 K. The cotunnite-type form was observed during compression between 54-117 GPa with additional laser heating carried out at 91 and 111 GPa. Fitting the pressure-volume data for the high-pressure phases to the second-order Birch-Murnaghan equation of state yields a bulk modulus of 259(26) GPa for the Pbca phase and 417(7) GPa for the cotunnite-type phase.We report x-ray photoelectron spectroscopy (XPS) study of Na and K adlayers on icosahedral Al{sub 70.5}Pd{sub 21}Mn{sub 8.5} (i-Al-Pd-Mn) quasicrystal. The Na 1s core-level exhibits a continuous linear shift of 0.8 eV towards lower binding energies (BE) with increasing coverage up to one monolayer (ML) saturation coverage. In the case of K/i-Al-Pd-Mn, a similar linear shift in the K 2p spectra towards lower BE is observed. In both cases, the plasmon related loss features are observed only above 1 ML. The substrate core-level peaks, such as Al 2p, do not exhibit any shift with the adlayer deposition up to the highest coverage. Based on these experimental observations and previous studies of alkali metal growth on metals, we conclude that below 1 ML, both Na and K form a dispersed phase on i-Al-Pd-Mn and there is hardly any charge transfer to the substrate. The variation of the adlayer and substrate core-level intensities with coverage indicates layer by layer growth.We report the magnetic properties of the ZnL{sub 2}S{sub 4} (L=Er,Tm,Yb) olivines, in which the magnetic lanthanide ions are in a potentially frustrated geometry consisting of sawtooth chains of corner-sharing triangles. Fits to the high-temperature magnetic susceptibility yielded Curie-Weiss temperatures of {theta}{sub W}{approx_equal}-4, -13, and -75 K for the Er, Tm, and Yb compounds, respectively. None of the compounds displayed magnetic long-range order above T=1.8 K. The lack of ordering at temperatures near {theta}{sub W} may be attributed to either the low dimensionality of the structure or the frustrating effect of the triangular geometry.

Three-dimensional organization of rare-earth atoms at grain boundaries in silicon nitride

Used in the preparation of Si3N4 components, rare-earth elements promote the growth of needlelike grains essential to elevated toughness; evidently, La is significantly more effective than Lu. To explore this difference, we determine the three-dimensional organization of rare-earth atoms in the amorphous phase near prismatic interfaces in La- and Lu-containing Si3N4 using aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and image processing. Evidence is presented for substantial atomic structure in notionally amorphous volumes. While the atomic arrangement in the amorphous phase conforms to the periodicity of the terminating crystal plane in both cases, the attachment sites are very different.

Controlled orientation of ellipsoidal fullerene C70 in carbon nanotubes

Density functional theory calculations predict two orientations for ellipsoidal C70 fullerenes inside single-walled carbon nanotubes (SWNTs) of different sizes: transverse orientation for C70 in (11,11) nanotubes (d=14.9 A) and longitudinal orientation for C70 in (10,10) nanotubes (d=13.6 A). SWNTs with these diameters have been prepared and filled with the C70 fullerenes, and characterized by Raman spectroscopy and high-resolution transmission electron microscopy, showing the orientations predicted by theory.

Phase stability of ternary fcc and bcc Fe-Cr-Ni alloys

The phase stability of fcc and bcc magnetic binary Fe-Cr, Fe-Ni, Cr-Ni alloys and ternary Fe-Cr-Ni alloys is investigated using a combination of density functional theory (DFT), Cluster Expansion (CE) and Magnetic Cluster Expansion (MCE). Energies, magnetic moments, and volumes of more than 500 alloy structures are evaluated using DFT, and the most stable magnetic configurations are compared with experimental data. Deviations from the Vegard law in fcc Fe-Cr-Ni alloys, associated with non-linear variation of atomic magnetic moments as functions of alloy composition, are observed. Accuracy of the CE model is assessed against the DFT data, where for ternary alloys the cross-validation error is smaller than 12 meV/atom. A set of cluster interaction parameters is defined for each alloy, where it is used for predicting new ordered alloy structures. Fcc Fe2CrNi phase with Cu2NiZn-like structure is predicted as the global ground state with the lowest chemical ordering temperature of 650K. DFT-based Monte Carlo (MC) simulations are used for assessing finite temperature fcc-bcc phase stability and order-disorder transitions in Fe-Cr-Ni alloys. Enthalpies of formation of ternary alloys calculated from MC simulations at 1600K combined with magnetic correction derived from MCE are in excellent agreement with experimental values measured at 1565K. Chemical order is analysed, as a function of temperature and composition, in terms of the Warren-Cowley short-range order (SRO) parameters and effective chemical pairwise interactions.

Arrangement of rare-earth elements at prismatic grain boundaries in silicon nitride

The arrangement of rare-earth atoms at {100} prism planes of La- and Lu-containing polycrystalline Si3N4 specimens is studied using high-angle annular dark-field scanning transmission electron microscopy. For both systems, the attachment sites of rare-earth atoms are well-defined and largely conform to the periodicity of the terminating plane of the Si3N4 grain. We observe significant differences between the structural arrangement of La and Lu atoms at the interface.

Atomistic modelling of TiAl I. Bond-order potentials with environmental dependence

Bond-order potentials (BOPs) for L10 TiAl have been developed and constructed within a tight-binding framework. In addition to the usual attractive bond-energy contribution arising from the formation of covalent bonds and pairwise contribution describing the overlap repulsion and electrostatic interaction, we have included an environmentally dependent term to represent the strong repulsion experienced by the valence sp electrons in transition metals and their alloys. The latter contribution is crucial for reproducing the negative Cauchy pressures of TiAl and other transition-metal-based intermetallic compounds. The constructed BOPs have been tested in the following ways: firstly, examination of the mechanical stability of the tetragonal L10 lattice with respect to large deformations and other crystal structures with the same stoichiometry; secondly, calculation of the γ surface for {111} and related evaluation of the energies of stacking-fault-type defects; thirdly, calculation of energies of the γ-γ interfaces that are present in the lamellar TiAl and energies associated with the formations of point defects in TiAl. The results of all these calculations show very good agreement with various ab-initio calculations. Importantly, we find that this potential is transferable to the different bonding environment in the hexagonal D019 Ti3Al. Hence these BOPs are suitable for atomistic study of dislocations and other extended defects not only in L10 TiAl but also in Ti3Al and possibly structures with other titanium-rich stoichiometries.

Metastability of the o-phase in transition-metal aluminides: First-principles structural predictions

Abstract A systematic total-energy study has been performed on the ω-phase of transition-metal-aluminide-based alloys using first-principles electronic structure calculations. The calculated o-phase heat of formation for ω-phase against the electron per atom ratio e/a is found to show the same trends as the measured diffuse ω peak for alloys with values of e/a between 3·3 and 4·7. Moreover, we predict that the ω-phase is the most stable amongst competing metastable phases for NbAl. ω collapse studies show a strong correlation between this transformation and a mechanical instability in the related B2 alloys at low temperatures. A partial ω-type shuffle is also predicted for Ni2Al alloys with e/a values close to 7 in the B82 structure type. As a result of these calculations, we are now able to study the phase diagrams of structurally important ternary alloys such as Ti[sbnd]Al[sbnd]V of Ti[sbnd]Al[sbnd]Nb.

Anatase-rutile phase transformation of titanium dioxide bulk material: a DFT + U approach.

The anatase-rutile phase transformation of TiO(2) bulk material is investigated using a density functional theory (DFT) approach in this study. According to the calculations employing the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional with the Vanderbilt ultrasoft pseudopotential, it is suggested that the anatase phase is more energetically stable than rutile, which is in variance with the experimental observations. Consequently, the DFT + U method is employed in order to predict the correct structural stability in titania from electronic-structure-based total energy calculations. The Hubbard U term is determined by examining the band structure of rutile with various values of U from 3 to 10 eV. At U = 5 eV, a theoretical bandgap for rutile is obtained as 3.12 eV, which is in very good agreement with the reported experimental bandgap. Hence, we choose the DFT + U method (with U = 5 eV) to investigate the transformation pathway using the newly-developed solid-state nudged elastic band (ss-NEB) method, and consequently obtain an intermediate transition structure that is 9.794 eV per four-TiO(2) above the anatase phase. When the Ti-O bonds in the transition state are examined using charge density analysis, seven Ti-O bonds (out of 24 bonds in the anatase unit cell) are broken, and this result is in excellent agreement with a previous experimental study (Penn and Banfield 1999 Am. Miner. 84 871-6).