Atomic structure and vibrational properties of icosahedral B4_4C boron carbide

The atomic structure of icosahedral B$_4$C boron carbide is determined by comparing existing infra-red absorption and Raman diffusion measurements with the predictions of accurate {\it ab initio} lattice-dynamical calculations performed for different structural models. This allows us to unambiguously determine the location of the carbon atom within the boron icosahedron, a task presently beyond X-ray and neutron diffraction ability. By examining the inter- and intra-icosahedral contributions to the stiffness we show that, contrary to recent conjectures, intra-icosahedral bonds are harder.Comment: 9 pages including 3 figures, accepted in Physical Review Letter

First-principles study on the intermediate compounds of LiBH4_4

We report the results of the first-principles calculation on the intermediate compounds of LiBH$_4$. The stability of LiB$_3$H$_8$ and Li$_2$B$_n$H$_n (n=5-12)$ has been examined with the ultrasoft pseudopotential method based on the density functional theory. Theoretical prediction has suggested that monoclinic Li$_2$B$_{12}$H$_{12}$ is the most stable among the candidate materials. We propose the following hydriding/dehydriding process of LiBH$_4$ via this intermediate compound : LiBH$_4 \leftrightarrow {1/12}$Li$_{2}$B$_{12}$H$_{12} + {5/6}$ LiH $+ {13/12}$H$_2 \leftrightarrow$LiH $+$ B $+ {3/2}$H$_2$. The hydrogen content and enthalpy of the first reaction are estimated to be 10 mass% and 56 kJ/mol H$_2$, respectively, and those of the second reaction are 4 mass% and 125 kJ/mol H$_2$. They are in good agreement with experimental results of the thermal desorption spectra of LiBH$_4$. Our calculation has predicted that the bending modes for the $\Gamma$-phonon frequencies of monoclinic Li$_2$B$_{12}$H$_{12}$ are lower than that of LiBH$_4$, while stretching modes are higher. These results are very useful for the experimental search and identification of possible intermediate compounds.Comment: 7 pages, 5 figures, submitted to PR

X-ray diffraction measurements of the c-axis Debye-Waller factors of YBa2Cu3O7 and HgBa2CaCu2O6

We report the first application of x-rays to the measurement of the temperature dependent Bragg peak intensities to obtain Debye-Waller factors on high-temperature superconductors. Intensities of (0,0,l) peaks of YBa2Cu3O7 and HgBa2CaCu2O6 thin films are measured to obtain the c-axis Debye-Waller factors. While lattice constant and some Debye-Waller factor measurements on high Tc superconductors show anomalies at the transition temperature, our measurements by x-ray diffraction show a smooth transition of the c-axis Debye-Waller factors through T$_c$. This suggests that the dynamic displacements of the heavy elements along the c-axis direction in these compounds do not have anomalies at Tc. This method in combination with measurements by other techniques will give more details concerning dynamics of the lattice.Comment: 4 pages, 2 figures. To be published in Physical Review B (Brief Report

Nuclear Inelastic X-Ray Scattering of FeO to 48 GPa

The partial density of vibrational states has been measured for Fe in compressed FeO (w\"ustite) using nuclear resonant inelastic x-ray scattering. Substantial changes have been observed in the overall shape of the density of states close to the magnetic transiton around 20 GPa from the paramagnetic (low pressure) to the antiferromagnetic (high pressure) state. Our data indicate a substantial softening of the aggregate sound velocities far below the transition, starting between 5 and 10 GPa. This is consistent with recent radial x-ray diffraction measurements of the elastic constants in FeO. The results indicate that strong magnetoelastic coupling in FeO is the driving force behind the changes in the phonon spectrum of FeO.Comment: 4 pages, 4 figure

A neutron scattering study of two-magnon states in the quantum magnet copper nitrate

We report measurements of the two-magnon states in a dimerized antiferromagnetic chain material, copper nitrate (Cu(NO3)2*2.5D2O). Using inelastic neutron scattering we have measured the one and two magnon excitation spectra in a large single crystal. The data are in excellent agreement with a perturbative expansion of the alternating Heisenberg Hamiltonian from the strongly dimerized limit. The expansion predicts a two-magnon bound state for q ~ (2n+1)pi*d which is consistent with the neutron scattering data.Comment: 11 pages of revtex style with 6 figures include

Generalized calculation of magnetic coupling constants for Mott-Hubbard insulators: Application to ferromagnetic Cr compounds

Using a Rayleigh-Schr\"odinger perturbation expansion of multi-band Hubbard models, we present analytic expressions for the super-exchange coupling constants between magnetic transition metal ions of arbitrary separation in Mott-Hubbard insulators. The only restrictions are i) all ligand ions are closed shell anions and ii) all contributing interaction paths are of equal length. For short paths, our results essentially confirm the Goodenough-Kanamori-Anderson rules, yet in general there does not exist any simple rule to predict the sign of the magnetic coupling constants. The most favorable situation for ferromagnetic coupling is found for ions with less than half filled d shells, the (relative) tendency to ferromagnetic coupling increases with increasing path length. As an application, the magnetic interactions of the Cr compounds Rb$_2$CrCl$_4$, CrCl$_3$, CrBr$_3$ and CrI$_3$ are investigated, all of which except CrCl$_3$ are ferromagnets.Comment: 13 pages, 6 eps figures, submitted to Phys Rev

On the brass- and silver-colored forms of PTGA{sub 2}

PtGa[sub 2] has previously been reported to exist as both a brass-colored, fluorite-structured phase and as a silver-colored alloy of unknown crystal structure. The crystal structure of the silver- colored form is reported here, along with a discussion of the stoichiometric factors responsible for the polymorphy of this phase. The silver- colored form belongs to the space group I4[SUB 1]/acd, with the lattice parameters a = 8.5544(4) and c = 21.574(17) Angstroms, and Z = 32. The structure consists of layers of Pt and Ga stacked along the c axis, in which two crystallographically different Pt and Ga atoms have similar environments involving eight and nine nearest neighbors, respectively. This structural arrangement may be the prototype for a family of ternary platinum metal-Group B-based phases. The present investigation also necessitates changes in the currently accepted Ga- Pt phase diagram. Stoichiometric PtGa[sub 2] undergoes a structural transformation upon cooling from a brass-colored fluorite structure to this silver-colored, tetragonal structure. However, the transformation is inhibited if the composition of the fluorite- structured phase is Ga-poor

Ion beam modification of Tl-Ba-Ca-Cu-O type high temperature superconductors during irradiation

Microstructural modification of high temperature superconductor (HTS) single-crystal plates of Tl-1212 and Tl-2212 (numbers designate the Tl/Ba/Ca/Cu cation ratio) was studied during 1.5 MeV Kr{sup +} and Xe{sup +} ion irradiation with in-situ electron diffraction and after ion irradiation with high resolution TEM (HRTEM). Similar in-situ temperature dependence effects are seen for both phases. During irradiations from 22K to 673K, an amorphous halo develops after very low ion dose or fluence (1.7 {times} 10{sup 12} ions/cm{sup 2}). During irradiation at 100 and 300K, complete amorphization is obtained, while at 22 and {ge}533K, the halo fades slightly and a polycrystalline ring pattern develops, indicating ion irradiation induced crystallization occurred. After a low ion dose (8.5 {times} 10{sup 12} ions/cm{sup 2}) at 100 and 300K, HRTEM reveals amorphous regions 5-20 nm in size which are not columnar and do not all penetrate the entire sample thickness. At 22 and {ge}533K, Moire fringes and misoriented crystallites of cascade size are observed. The 4-6nm crystallites are thallium-rich

XRAYL: a program for producing idealized powder diffraction line profiles from overlapped powder patterns

The X-ray diffraction patterns of samples of polycrystalline materials are used to identify and characterize phases. Very often the total (or composite) profile consists of a series of overlapping profiles. In many applications it is necessary to separate the component profiles from the total profile. (In this document the terms {ital profile, line}, and {ital peak} are used interchangeably to represent these features of X-ray or neutron diffraction patterns.) A computer program, XRAYL, first developed in the 1980s and subsequently enlarged and improved, allows the fitting of analytical functions to powder diffraction lines. The fitting process produces parameters of chosen profile functions, diffraction line by diffraction line. The resulting function parameters may then be used to generate ``idealized`` powder diffraction lines as counts at steps in 2{Omega}. The generated lines are effectively free of statistical noise and contributions from overlapping lines. Each separated line extends to background on both sides of the generated profile. XRAYL may, therefore, be used in X-ray powder diffraction profile analysis as a preprocessor program that is, separating peaks and feeding the ``resolved`` data to subsequent analysis programs. This self- contained document includes: (1) a description of the fitting functions coded into XRAYL, (2) an outline of the least-squares algorithm used in fitting the profile function, (3) the file formats and contents utilized by the computer code, (4) the user options and their presentation requirements for execution of the program, (5) an example of input and output for a test case, and (6) source code listings on a diskette

Neutron diffraction studies on recrystallization of solution derived lead zirconate titanates

We performed neutron powder diffraction on solution-derived lead zirconate titanates (PZT). Three compositions, PZT 45/55, PZT 20/80 and PbTiO{sub 3}, were investigated. The materials were annealed so that the perovskite phase had just begun to grow from the precursor phase. In our materials this precursor phase is the pyrochlore rather than fluorite phase. The results show that in the pyrochlore phase, the (Ti,Zr) and the Pb are ordered in their crystallographic sites while the O are essentially disordered in both of the two usual pyrochlore anion sites