Time-Dependent Density Functional Theory with Ultrasoft Pseudopotential: Real-Time Electron Propagation across Molecular Junction

A practical computational scheme based on time-dependent density functional theory (TDDFT) and ultrasoft pseudopotential (USPP) is developed to study electron dynamics in real time. A modified Crank-Nicolson time-stepping algorithm is adopted, under planewave basis. The scheme is validated by calculating the optical absorption spectra for sodium dimer and benzene molecule. As an application of this USPP-TDDFT formalism, we compute the time evolution of a test electron packet at the Fermi energy of the left metallic lead crossing a benzene-(1,4)-dithiolate junction. A transmission probability of 5-7%, corresponding to a conductance of 4.0-5.6muS, is obtained. These results are consistent with complex band structure estimates, and Green's function calculation results at small bias voltages

Charge-Induced Fragmentation of Sodium Clusters

The fission of highly charged sodium clusters with fissilities X>1 is studied by {\em ab initio} molecular dynamics. Na_{24}^{4+} is found to undergo predominantly sequential Na_{3}^{+} emission on a time scale of 1 ps, while Na_{24}^{Q+} (5 \leq Q \leq 8) undergoes multifragmentation on a time scale \geq 0.1 ps, with Na^{+} increasingly the dominant fragment as Q increases. All singly-charged fragments Na_{n}^{+} up to size n=6 are observed. The observed fragment spectrum is, within statistical error, independent of the temperature T of the parent cluster for T \leq 1500 K. These findings are consistent with and explain recent trends observed experimentally.Comment: To appear in Physical Review Letter

Irreversible Structural Transformation of five fold i-AlPdMn Quasicrystals after Ion Bombardment and Annealing

Five fold i-AlPdMn surface prepared under UHV by ion bombardment and annealing was so far considered to be bulk terminated. This result was substantially based on a quantitative LEED analyses [1]. Analysis of the specular rod in a X ray diffraction experiment at grazing incidence supported this result [2]. We present a new study of this surface by high resolution X ray diffraction at normal incidence. In this Bragg configuration the diffraction peak 18 – 29 for instance is at a photon energy of 2.873keV, the 72 – 116 reflection at 5.725keV. This results in an analyzed thickness of the sample surface of a few micrometers. The surface was cleaned by ion bombardment. During annealing (T≅880K), we clearly observed the progressive disappearance of the initial Bragg peak characteristic of the as cast bulk sample. Conversely a new Bragg peak grows at an energy position shifted by 1eV compared to the position of the original Bragg peak. This is a clear signature for an irreversible structural transformation which takes place on at least the micron thickness. On the transformed surface, both, a LEED pattern and a RHEED pattern, characteristic for a five fold surface were easily obtained. This high resolution experiment (the relative Bragg peak shift is 3ׁ10−4) was reproduced on samples from different initial compositions. This shows that five fold i-AlPdMn surface changes after preparation by ion bombardment and annealing at 900K on a micrometer thickness. This is not consistent with the conclusion that the surface is simply terminated by a cut of the original bulk. We conclude that a reorganization process of the quasicrystalline structure during annealing proceeds in the surface vicinity (probed depth is close to a few microns)

An exact stochastic mean-field approach to the fermionic many-body problem

We investigate a reformulation of the dynamics of interacting fermion systems in terms of a stochastic extension of Time Dependent Hartree-Fock equations. The noise is found from a path-integral representation of the evolution operator and allows to interpret the exact N-body state as a coherent average over Slater determinants evolving under the random mean-fied. The full density operator and the expectation value of any observable are then reconstructed using pairs of stochastic uncorrelated wave functions. The imaginary time propagation is also presented and gives a similar stochastic one-body scheme which converges to the exact ground state without developing a sign problem. In addition, the growth of statistical errors is examined to show that the stochastic formulation never explode in a finite dimensional one-body space. Finally, we consider initially correlated systems and present some numerical implementations in exactly soluble models to analyse the precision and the stability of the approach in practical cases

Coupled structural and magnetic properties of ferric fluoride nanostructures part I: a Metropolis atomistic study

A modified Metropolis atomistic simulation is proposed to model the structure of grain boundaries (GBs) and interfaces in ionic nanostructured systems and is applied to the magnetically interesting case of iron trifluoride (FeF3). We chose long-range interatomic potentials adjusted on experimental results, and adapted a previously established Monte Carlo scheme consisting of various modifications of the simulated annealing/ Metropolis algorithm. Atomic structures of twisted and tilted GBs as a function of the relative disorientation of the grains have been achieved yielding close to experimentally measured properties. This approach takes into account the structure of the grains far from the interface in order to constrain the relative orientation of the grains, without any periodic boundary conditions. One concludes that a long-range coulombic falloff of the interatomic potentials is necessary to obtain GB structures presenting a correct local topology but with a smooth transition from crystalline to amorphous states. The structural features are finally discussed in terms of topological aspects and local magnetic structure.Comment: submitted to JMM

High-Accuracy X-Ray Diffraction Analysis of Phase Evolution Sequence During Devitrification of Cu50Zr50 Metallic Glass

Real-time high-energy X-ray diffraction (HEXRD) was used to investigate the crystallization kinetics and phase selection sequence for constant-heating-rate devitrification of fully amorphous Cu50Zr50, using heating rates from 10 K/min to 60 K/min (10 °C/min to 60 °C/min). In situ HEXRD patterns were obtained by the constant-rate heating of melt-spun ribbons under synchrotron radiation. High-accuracy phase identification and quantitative assessment of phase fraction evolution though the duration of the observed transformations were performed using a Rietveld refinement method. Results for 10 K/min (10 °C/min) heating show the apparent simultaneous formation of three phases, orthorhombic Cu10Zr7, tetragonal CuZr2 (C11b), and cubic CuZr (B2), at 706 K (433 °C), followed immediately by the dissolution of the CuZr (B2) phase upon continued heating to 789 K (516 °C). Continued heating results in reprecipitation of the CuZr (B2) phase at 1002 K (729 °C), with the material transforming completely to CuZr (B2) by 1045 K (772 °C). The Cu5Zr8 phase, previously reported to be a devitrification product in C50Zr50, was not observed in the present study

Métallurgie des phases icosaédriques

Quasicrystalline phases have been discovered in numerous alloy systems. This paper gives a short introductory review on some aspects of quasicrystal metallurgy. From metastable quasicrystal phases to highly perfect icosahedral single grains, spectacular progress in the structural quality of the samples has led to understand how quasicrystal behaviour differs from that of other phases. This knowledge now is used to optimize the specific charactenstics in the field of the electronic properties

Calculation of phase diagrams for the order-disorder transition in the binary systems Ni-Fe and Ni-Al

The Cluster Variation Method, in the Tetrahedron-Octahedron approximation, is used to investigate the Ni3Al and Ni3Fe ordering phase diagrams. The pairwise interaction potentials used are extracted from X-ray or neutron diffuse scattering measurements. The calculated phase diagrams are compared to the experimental data. It is shown that, for the case of Ni3Fe, a satisfactory agreement can be achieved by introducing a slight variation of the second-neighbor pair interaction potential as a function of concentration.La Méthode de Variation des Amas, dans l'approximation du Tétraèdre-Octaèdre, est utilisée pour étudier le diagramme d'équilibre des phases au voisinage de la transition ordredésordre, pour Ni3Al et Ni3Fe. Les potentiels d'interaction de paires sont déterminés à partir de mesures de diffusion diffuse des rayons X ou des neutrons. Les diagrammes de phase calculés sont comparés aux données expérimentales. On montre que, dans le cas de Ni3Fe, un accord satisfaisant peut être obtenu en introduisant une faible variation du potentiel d'interaction de paires de seconds voisins en fonction de la concentration

Ternary coherent phase diagram on the FCC lattice

In this paper, we describe a general and original method to study the ground state problem, in multicomponent systems. The method is illustrated by considering the nearest neighbour Ising model in ternary FCC lattices, and leads to the occurrence as a ground state of a new phase called L'. The ternary coherent phase diagram is then calculated within the CVM tetrahedron approximation, showing Chat the L' phase displays a stability domain as large as those of the L1$_0$ and L1$_2$ domains. At low but non-zero temperature, a "quaternary ground state" phase, called L", stabilized by entropy effects, appears in the phase diagram