Effect of relaxation on the oxygen K-edge electron energy-loss near-edge structure in yttria-stabilized zirconia

The electron energy-loss near-edge structure (ELNES) at the oxygen K-edge has been investigated in a range of yttria-stabilized zirconia (YSZ) materials. The electronic structure of the three polymorphs of pure ZrO2 and of the doped YSZ structure close to the 33 mol %Y2O3 composition have been calculated using a full-potential linear muffin-tin orbital method (NFP-LMTO) as well as a pseudopotential based technique. Calculations of the ELNES dipole transition matrix elements in the framework of the NFP-LMTO scheme and inclusion of core hole screening within Slater's transition state theory enable the ELNES to be computed. Good agreement between the experimental and calculated ELNES is obtained for pure monoclinic ZrO2. The agreement is less good with the ideal tetragonal and cubic structures. This is because the inclusion of defects is essential in the calculation of the YSZ ELNES. If the model used contains ordered defects such as vacancies and metal Y planes, agreement between the calculated and experimental O K-edges is significantly improved. The calculations show how the five different O environments of Zr,Y,O, are connected with the features observed in the experimental spectra and demonstrate clearly the power of using ELNES to probe the stabilization mechanism in doped metal oxides.

The near-edge structure in energy-loss spectroscopy: many-electron and magnetic effects in transition metal nitrides and carbides

We investigate the ability of the local density approximation (LDA) in density functional theory to predict the near-edge structure in electron energy-loss spectroscopy in the dipole approximation. We include screening of the core hole within the LDA using Slater's transition state theory. We find that anion K-edge threshold energies are systematically overestimated by 4.22 +/- 0.44 eV in twelve transition metal carbides and nitrides in the rock-salt (B1) structure. When we apply this 'universal' many-electron correction to energy-loss spectra calculated within the transition state approximation to LDA, we find quantitative agreement with experiment to within one or two eV for TiC, TiN and VN. We compare our calculations to a simpler approach using a projected Mulliken density which honours the dipole selection rule, in place of the dipole matrix element itself. We find remarkably close agreement between these two approaches. Finally, we show an anomaly in the near-edge structure in CrN to be due to magnetic structure. In particular, we find that the N K edge in fact probes the magnetic moments and alignments of ther sublattice.

Entanglement between two superconducting qubits via interaction with nonclassical radiation

We propose a scheme to physically interface superconducting nanocircuits and quantum optics. We address the transfer of quantum information between systems having different physical natures and defined in Hilbert spaces of different dimensions. In particular, we investigate the transfer of the entanglement initially in a nonclassical state of an infinite dimensional system to a pair of superconducting charge qubits. This setup is able to drive an initially separable state of the qubits into an almost pure, highly entangled state suitable for quantum information processing.

Nonlinear response of permanent dipoles in a uniaxial potential to alternating fields

It is shown how the existing theory of the dynamic Kerr effect and nonlinear dielectric relaxation based on the noninertial Brownian rotation of noninteracting rigid dipolar particles may be generalized to take into account interparticle interactions using the Maier-Saupe mean field potential. The results (available in simple closed form) suggest that the frequency dependent nonlinear response provides a method of measuring the Kramers escape rate (or in the analogous problem of magnetic relaxation of fine single domain ferromagnetic particles, the superparamagnetic relaxation time).

Microscopic models for dielectric relaxation in disordered systems

It is shown how the Debye rotational diffusion model of dielectric relaxation of polar molecules (which may be described in microscopic fashion as the diffusion limit of a discrete time random walk on the surface of the unit sphere) may be extended to yield the empirical Havriliak-Negami (HN) equation of anomalous dielectric relaxation from a microscopic model based on a kinetic equation just as in the Debye model. This kinetic equation is obtained by means of a generalization of the noninertial Fokker-Planck equation of conventional Brownian motion (generally known as the Smoluchowski equation) to fractional kinetics governed by the HN relaxation mechanism. For the simple case of noninteracting dipoles it may be solved by Fourier transform techniques to yield the Green function and the complex dielectric susceptibility corresponding to the HN anomalous relaxation mechanism.

Vibrational properties of nanometric AB(2) ionic clusters

A broad survey of harmonic dynamics in AB(2) clusters with up to N = 3000 atoms is performed using a simple rigid ion model, with ionic radii selected to give rutile as the ground state structure for the corresponding extended crystal. The vibrational density of states is already close to its bulk counterpart for N similar to 500, with characteristic differences due to surfaces, edges and vertices. Two methods are proposed and tested to map the cluster vibrational states onto the rutile crystal phonons. The net distinction between infrared (IR) active and Raman active modes that exists for bulk rutile becomes more and more blurred as the cluster size is reduced. It is found that, in general, the higher the IR activity of the mode, the more this is affected by the system size. IR active modes are found to spread over a wide frequency range for the finite clusters. Simple models based on either a crude confinement constraint or surface pressure arguments fail to reproduce the results of the calculations. The effects of the stoichiometry and dielectric properties of the surrounding medium on the vibrational properties of the clusters are also investigated.

Surface alloying and mixing at the Mn/Fe(001) interface: Real-time photoelectron spectroscopy and modified embedded atom simulations

Structural and magnetic properties of thin Mn films on the Fe(001) surface have been investigated by a combination of photoelectron spectroscopy and computer simulation in the temperature range 300 Kless than or equal toTless than or equal to750 K. Room-temperature as deposited Mn overlayers are found to be ferromagnetic up to 2.5-monolayer (ML) coverage, with a magnetic moment parallel to that of the iron substrate. The Mn atomic moment decreases with increasing coverage, and thicker samples (4-ML and 4.5-ML coverage) are antiferromagnetic. Photoemission measurements performed while the system temperature is rising at constant rate (dT/dtsimilar to0.5 K/s) detect the first signs of Mn-Fe interdiffusion at T=450 K, and reveal a broad temperature range (610 Kless than or equal toTless than or equal to680 K) in which the interface appears to be stable. Interdiffusion resumes at Tgreater than or equal to680 K. Molecular dynamics and Monte Carlo simulations allow us to attribute the stability plateau at 610 Kless than or equal toTless than or equal to680 K to the formation of a single-layer MnFe surface alloy with a 2x2 unit cell and a checkerboard distribution of Mn and Fe atoms. X-ray-absorption spectroscopy and analysis of the dichroic signal show that the alloy has a ferromagnetic spin structure, collinear with that of the substrate. The magnetic moments of Mn and Fe atoms in the alloy are estimated to be 0.8mu(B) and 1.1mu(B), respectively.

Path-integral study of a two-dimensional Lennard-Jones glass

The glass transition in a quantum Lennard-Jones mixture is investigated by constant-volume path-integral simulations. Particles are assumed to be distinguishable, and the strength of quantum effects is varied by changing h from zero (the classical case) to one (corresponding to a highly quantum-mechanical regime). Quantum delocalization and zero point energy drastically reduce the sensitivity of structural and thermodynamic properties to the glass transition. Nevertheless, the glass transition temperature T-g can be determined by analyzing the phase space mobility of path-integral centroids. At constant volume, the T-g of the simulated model increases monotonically with increasing h. Low temperature tunneling centers are identified, and the quantum versus thermal character of each center is analyzed. The relation between these centers and soft quasilocalized harmonic vibrations is investigated. Periodic minimizations of the potential energy with respect to the positions of the particles are performed to determine the inherent structure of classical and quantum glassy samples. The geometries corresponding to these energy minima are found to be qualitatively similar in all cases. Systematic comparisons for ordered and disordered structures, harmonic and anharmonic dynamics, classical and quantum systems show that disorder, anharmonicity, and quantum effects are closely interlinked.

Equilibrium structure of erbium-oxygen complexes in crystalline silicon

The equilibrium structure of ErOn (nless than or equal to6) complexes in crystalline silicon has been investigated by density-functional computations. Two different geometries have been considered, corresponding to the substitutional and tetrahedral interstitial site for erbium. All atomic coordinates have been optimized by Car-Parrinello molecular dynamics. The resulting structures have low symmetry, with E-O distances of similar to2.35 Angstrom. The substitutional site is the most stable one for nless than or equal to2, while the tetrahedral interstitial is favored for n>2.

Fixed-node diffusion Monte Carlo computations for closed-shell jellium spheres

Fixed-node diffusion Monte Carlo computations are used to determine the ground state energy and electron density for jellium spheres with up to N = 106 electrons and background densities corresponding to the electron gas parameter 1 less than or equal to r(s)less than or equal to5.62. We analyze the density and size dependence of the surface energy, and we extrapolate our data to the thermodynamic limit. The results agree well with the predictions of density functional computations using the local density approximation. In the case of N = 20, we extend our computation to higher densities and identify a transition between atomic- and jelliumlike nodal structures occurring at the background density corresponding to r(s)=0.13. In this case the local density approximation is unable to reproduce the changes in the correlation energy due to the discontinuous transition in the ground state nodal structure. We discuss the relevance of our results for nonlocal approximations to density functional theory.

Simple models of complex aggregation: Vesicle formation by soft repulsive spheres with dipolelike interactions

Structural and thermodynamic properties of spherical particles carrying classical spins are investigated by Monte Carlo simulations. The potential energy is the sum of short range, purely repulsive pair contributions, and spin-spin interactions. These last are of the dipole-dipole form, with however, a crucial change of sign. At low density and high temperature the system is a homogeneous fluid of weakly interacting particles and short range spin correlations. With decreasing temperature particles condense into an equilibrium population of free floating vesicles. The comparison with the electrostatic case, giving rise to predominantly one-dimensional aggregates under similar conditions, is discussed. In both cases condensation is a continuous transformation, provided the isotropic part of the interatomic potential is purely repulsive. At low temperature the model allows us to investigate thermal and mechanical properties of membranes. At intermediate temperatures it provides a simple model to investigate equilibrium polymerization in a system giving rise to predominantly two-dimensional aggregates.

Current-induced transition in atomic-sized contacts of metallic alloys

We have measured conductance histograms of atomic point contacts made from the noble-transition-metal alloys CuNi, AgPd, and AuPt for a concentration ratio of 1:1. For all alloys these histograms at low-bias voltage (below 300 mV) resemble those of the noble metals, whereas at high bias (above 300 mV) they resemble those of the transition metals. We interpret this effect as a change in the composition of the point contact with bias voltage. We discuss possible explanations in terms of electromigration and differential diffusion induced by current heating.

Thin Ta films: growth, stability, and diffusion studied by molecular-dynamics simulations

We report results of classical molecular-dynamics simulations of bcc and beta-Ta thin films. Thermal PVD film growth, surface roughness, argon ion bombardment, phase stability and transformation, vacancy and adatom diffusion, and thermal relaxation kinetics are discussed. Distinct differences between the two structures are observed, including a complex vacancy diffusion mechanism in beta-Ta. Embedded atom method potentials, which were fitted to bcc properties, have been used to model the Ta-Ta interactions. In order to verify the application of these potentials to the more complex beta-Ta structure, we have also performed density functional theory calculations. Results and implications of these calculations are discussed.

Anisotropic optical properties of arrays of gold nanorods embedded in alumina

A series of thin films comprising gold nanorods embedded in an alumina matrix have been fabricated with lengths ranging from 75 to 330 nm. Their optical properties, expressed in terms of extinction - In(T), where T is optical transmittance, have been measured as a function of wavelength, rod length, angle of incidence, and incident polarization state. The results are compared to a Maxwell-Garnett based theory modified to take into account the strongly anisotropic nature of the medium. Transverse and longitudinal plasmon resonances are observed. The interaction between the nanorods leads to the splitting of the longitudinal resonance with the longer-wavelength resonance being forbidden for direct optical observations. The shorter-wavelength resonance related to the symmetric coupling between longitudinal plasma excitations in the nanorods depends on rod length, polarization state, and angle of incidence of the probing light. The impact of electron confinement on the optical properties of the gold rods is also seen and may be incorporated into the Maxwell-Garnett theory by restricting the mean free path of the conduction electrons to produce excellent agreement between observations and the complete theory. Annealing experiments that modify the physical structure of the gold confirm this conclusion.