Electron density distribution in Si and Ge using multipole, maximum entropy method and pair distribution function analysis

The local, average and electronic structure of the semiconducting materials Si and Ge has been studied using multipole, maximum entropy method (MEM) and pair distribution function (PDF) analyses, using X-ray powder data. The covalent nature of bonding and the interaction between the atoms are clearly revealed by the two-dimensional MEM maps plotted on (100) and (110) planes and one-dimensional density along [100], [110] and [111] directions. The mid-bond electron densities between the atoms are 0.554 e/?³ and 0.187 e/?³ for Si and Ge respectively. In this work, the local structural information has also been obtained by analyzing the atomic pair distribution function. An attempt has been made in the present work to utilize the X-ray powder data sets to refine the structure and electron density distribution using the currently available versatile methods, MEM, multipole analysis and determination of pair distribution function for these two systems.      

Non-nuclear maxima (NNM), symmetric and asymmetric charge distribution in solar grade Si and n-GaAs, using X-ray powder data

The symmetric and asymmetric charge distribution of bonding electrons in silicon and gallium arsenide has been studied using experimental powder X-ray data sets. The mid-bond electron densities from the origin are found to be 0.787 and 1.725 e/ų at 1.175 and 1.222 Å, respectively, for Si and n-GaAs. The effectiveness of powder data sets in precise bonding studies has been verified. Multipole analysis of the valence charge distribution has also been done. The thermal vibration parameters have been studied and presented for both these systems. The magnitudes of the non-nuclear maxima of both these systems are consistent with those obtained using single-crystal studies.     

Pressure dependence of the electron density in solid iodine by the maximum-entropy method

Abstract

A direct observation of the electron density of solid iodine has been attempted in order to study the electron-density delocalization process due to pressure-induced metallization. A high-accuracy x-ray powder diffraction measurement was carried out with a diamond anvil cell and an imaging plate on a synchrotron-radiation source. The maximum entropy method was employed to analyze the data and to obtain electron-density maps under pressures up to 20 GPa. The electron density between adjacent iodine molecules has been shown to gradually increase with increasing pressure; also, a two-dimensional network is formed at a density level of 0.2 e/ų at around 16 GPa.     

Electron momentum density, band structure, and structural properties of SrS

The electron momentum density, the electronic band structure, and the structural properties of SrS are presented in this paper. The isotropic Compton profile, anisotropies in the directional Compton profiles, the electronic band structure and density of states are calculated using the ab initio periodic linear combination of atomic orbitals method with the CRYSTAL06 code. Structural parameters of SrS—lattice constants and bulk moduli in the B1 and B2 phases—are computed together with the transition pressure. The computed parameters are well in agreement with earlier investigations. To compare the calculated isotropic Compton profile, measurement on polycrystalline SrS is performed using 5Ci-²⁴¹Am Compton spectrometer. Additionally, charge transfer is studied by means of the Compton profiles computed from the ionic model. The nature of bonding in the isovalent SrS and SrO compounds is compared on the basis of equal-valenceelectron-density profiles and the bonding in SrS is found to be more covalent than in SrO.     

Synthesis and characterization of Ce-doped SrS phosphors

SrS:Ce phosphor was prepared by a solid-state diffusion method. Powder X-ray diffraction, transmission electron microscopy, and thermogravimetric analysis were used to characterize the as-prepared product, and the optical properties were studied by photoluminescence spectra. In addition, thermoluminescence and electron spin resonance studies have been carried out on SrS:Ce phosphor. The TL glow curve is broad and indicates two dominant peaks at 137 and 275^°C, with an additional peak, not clearly resolved, appearing as shoulder at ～362^°C. Two defect centers are observed at room temperature. One of them is characterized by an isotropic g-value of 2.0039 and is assigned to an F⁺ center. Step annealing measurements indicate a possible association between the F⁺ center and the 137^°C TL peak.     

An investigation on the bonding in MgO,CaO, SrO and BaO from the MEM electron density distributions

The bonding in MgO, CaO, SrO and BaO has been studied using the electron density distribution maps obtained utilizing the reported X-ray data by the statistical approach maximum entropy method (MEM). The ionic/covalent nature of the bonding and the interaction between the atoms are clearly revealed by the maps. The bonding in these systems is shown two-dimensionally on the (100) and (110) planes and the one-dimensional electron density profiles along (100), (110) and (111) directions have also been plotted using MEM electron densities. The electron density at the saddle point between the ions has been estimated using these profiles and compared with the available reported results. The resolution of these maps is high and hence these maps can be regarded as the most precise electron density distributions seen inside the chosen materials. The electron content of the doubly ionic oxygen and the cations are estimated from the three-dimensional MEM electron densities by assuming spheres of various radii. The histograms drawn with [F_Mem(k)−F_Obs(k)]/σ(k) versus the number of reflections show the validity of the approach and the appropriateness of the Gaussian weighting scheme used in the analysis.     

Covalent bonds in AlMnSi icosahedral quasicrystalline approximant

Electron density distributions were obtained using the maximum entropy method with synchrotron radiation powder data. In the metallic Al12Re, metallic bonding was observed for the icosahedral Al12 cluster with central Re atom. In the nonmetallic alpha-AlMnSi 1/1 approximant, covalent bonds were found in the electron density distribution of the Mackay icosahedral cluster without central atom. Rather than the Hume-Rothery mechanism, the covalency of Al (Si) icosahedron and that between Al (Si) and Mn atoms is considered to be the origin of the pseudogap and nonmetallic behavior of alpha-AlMnSi.     

Structural analysis of nano-sized-Pd/ZrO2 composite after H(D) absorption

Structural analysis of high density H(D) absorbed Pd particles with 5 nm dispersed ZrO₂ has been carried out using XAFS (X-ray Absorption Fine Structure) techniques. X-ray absorption spectra around the Pd K-absorption edge were observed and analyzed. The Pd–Pd bonding distance was enlarged by 0.08 Å during absorption of deuterium, and it completely reverted to its original state with the release of deuterium while maintaining the crystal lattice symmetry. These changes provide evidence that deuterium locates not on the surface of the Pd particle, but rather within the Pd crystal lattice. The hydrogen absorption mechanism will also be discussed.     

Structure and electron density analysis of oxide spinel LiTi2O4

The structure and electron density distribution of the superconducting spinel LiTi₂O₄ have been studied by the maximum entropy method using single crystal X-ray diffraction data at 293 K. The structure refinement confirmed the normal spinel cation distribution, Cubic, Fd-3m, a=8.4067(5) Å, and oxygen parameter u=0.26280(8). From the results of the MEM analysis using 228 independent reflections in the range of $\text{sin}\text{θ/λ<1.3}\text{A}\text{̊}{}^{\mathrm{-1}}\text{,}$ the strong covalent bonding was clearly found between Ti and O atoms, while no bonding was observed around Li atoms. We also calculated the electron density of the cubic spinel LiTi₂O₄ using first principles full-potential linearized augmented-plane-wave method. The electron density obtained experimentally is in good agreement with the theoretical one.     

Photoluminescence of SrS: Cu phosphors

Results of the investigation on the spectral characteristics of PL of SrS:Cu phosphors are presented. Probable emitters for the three observed bands, viz. 4710 Å, 5200 Å and 5480 Å, have been suggested.     

Structure Studies of Platinothioneins by Using Extended X-Ray Absorption Fine Structure Spectroscopy

The metal binding sites in the two Pt containing metallothioneins (Pt₇MT and Pt₁₄MT) were examined by means of Pt(II) L₃-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. Comparisons between the phase and amplitude functions derived from the isolated shells to those of Pt…Pt, Pt-S and Pt-N model components showed that each platinum in Pt₇MT was coordinated by four sulfur atoms at a distance of 2.31±0.01 Å. Analysis of the outer shell data of platinum atom in Pt⁷MT indicated backscattering platinum atom at approximate 4.29 Å. Strikingly different structural parameters had been obtained for the Pt¹⁴MT species, fitting of the first shell revealed that each platinum was coordinated by two sulfurs at the distance of 2.30±0.02 Å and two nitrogens at 2.02±0.02 Å. The results of the work provided the detailed information concerning the local environments of the coordinated Pt(II) in these two platinothioneins.     

Atomic-scale X-ray structural analysis of self-assembled monolayers on Silicon

Two related self-assembled monolayers (SAMs), 4-bromostyrene (BrSty) and 4-bromophenylacetylene (BPA), are photochemically grown from solution on to the monohydride-terminated Si(111) surface. The atomic-scale structures of the resulting SAMs are examined by X-ray standing waves (XSW), X-ray reflectivity (XRR), X-ray fluorescence, atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). The coverage is 0.5 ML. The results show that in each case the molecule covalently bonds to a single Si T₁ site and stands up-right with a slight molecular tilt of 17^○ that leaves the Br terminal end over a neighboring T₄ site. The Br height is 8.5?Å (BrSty) and 8.6?Å (BPA) above the top surface Si atom. The combined XSW and XRR results rule-out two alternative bonding models predicted by DFT that have the root of the molecule bonded to two neighboring top Si surface atoms. Based on the XSW 111 and 333 coherent fractions, the BPA/Si(111) has a reduced vertical Br distribution width in comparison to BrSty. This greater rigidity in the molecular structure is correlated to a C=C bond at the root.     

Observation of line radiation from highly charged Mo ions in a vacuum-spark plasma

Using a curved-crystal spectrograph of the transmission type the X-ray emission from a low-inductance vacuum-spark with Mo-electrodes has been investigated in the wavelength range 0.5Å<λ}<0.9Å. By means of a noise suppression technique, a number of weak lines have been resolved from the continuum. Comparing the measured wavelengths to results of relativistic energy level calculations these lines are identified as belonging to electronic transitions within singly excited heliumlike MoXLI ions and doubly excited lithiumlike MoXL ions. Continuum and line emission are used to estimate electron temperature and density.     

Theoretical studies of the bonding of sulfur to models of the (100) surface of nickel

Electronic wavefunctions have been obtained as a function of geometry for a S atom bonded to Ni clusters consisting of 1 to 4 atoms designed to model bonding to the Ni(100) surface. Electron correlation effects were included using the generalized valence bond and configuration interaction methods. Modeling the (100) surface with four Ni atoms, we find the optimum S position to be 1.33 Å above the surface, in good agreement with the value (1.30 ± 0.10 Å) from dynamic LEED intensity calculations. The bonding is qualitatively like that in H₂S with two covalent bonds to one diagonal pair of Ni atoms. There is a S pπ pair overlapping the other diagonal pair of Ni atoms. [Deleting this pair the S moves in to a position 1.04 Å from the surface.] There are two equivalent such structures, the resonance leading to equivalent S atoms and a c(2 × 2) structure for the S overlayer. The Ni in the layer beneath the surface seems to have little effect (~0.03 Å) on the calculated geometry. Bonding the S directly above a single Ni atom leads to a much weaker bond (D_e = 3.32 eV) than does bonding in a bridge position (D_e = 5.37 eV).     

Synthesis and Structural Characterization of a New Phase of GaAsO 4

A new polymorph of GaAsO 4 has been synthesised at high pressure and temperature (60 kbar and 1273 K). Samples were characterised by powder X-ray diffraction, scanning electron microscopy and EDAX spectroscopy. This material shows an hexagonal symmetry with cell parameters, a =8.1931(4) Å and c =4.3744(2) Å; particles are of hexagonal shape with a narrow size distribution around 2-3 w m and composition close to the Ga:As atomic ratio=1:1. This new high pressure phase of GaAsO 4 represents a new transition path for the ABO 4 compounds.     

Effect of uniaxial pressure on the Raman spectra of fluoro perovskites containing manganese with sodium or potassium

ABSTRACT

Perovskite structured mixed metal fluorides containing manganese/sodium or potassium have been synthesized in pure form by a greener precipitation route and characterized by high-resolution powder X-ray diffraction and Raman spectroscopy techniques. While all the reflections in the powder X-ray diffraction pattern of potassium manganese fluoride could be indexed in cubic symmetry with a = 4.1889 Å, sodium manganese fluoride showed reflections at positions typical of orthorhombic symmetry (Pnma space group) with a = 5.751, b = 8.008, and c = 5.548 Å. Potassium manganese fluoride in powder form showed bands at 209, 291, 386, 558, 621, and 733 cm^?1 in the Raman spectrum at room temperature. All these bands disappeared and second-order band at 1151 and 1298 cm^?1 emerged when the powders were compacted under pressure ranging between 1 and 4 tons (uniaxial). A similar change was noticed for sodium manganese fluoride in which bands at 1099, 1149, 1203, and 1286 cm^?1 were observed for the compacted samples. The response of the vibrational modes of these compounds to uniaxial pressure revealed the existence of large structural disorder in them. Additionally, the need for the extreme care to collect and interpret Raman data of polycrystalline samples of these systems has been illustrated through this study.     

Pressure-dependent phase transition in the ordered BaBi0.7Nb0.3O3 perovskite

BaBi_0.7Nb_0.3O₃, an ordered perovskite, crystallizes in a centrosymmetric rhombohedral structure with the space group R3¯. The refined cell parameters obtained from synchrotron powder X-ray diffraction data for the rhombohedral phase at ambient pressure are a=6.109 (2) Å and α=60.3 (1)°. The pressure-dependent synchrotron powder X-ray diffraction studies show a phase transition around 8.44±1 GPa, where it transforms from rhombohedral structure to a monoclinic structure. The lattice parameters obtained for the monoclinic phase at a pressure of 15±1 GPa are a=5.91 (2) Å, b=6.25 (3) Å and c=8.22 (1) Å with monoclinic angle, β=88 (1)°.     

Local structure of the high-temperature thermoelectric material PbTe using the maximum entropy method (MEM) and pair distribution function (PDF)

The electron density distribution and the local structure of the high temperature thermoelectric material PbTe has been studied. Powder X-ray data set of PbTe is analyzed in terms of cell parameter, thermal vibration parameters, 1D, 2D and 3-dimensional electron density distributions. The bonding between the atoms using the maximum entropy method (MEM) and bond-length distribution using pair distribution function (PDF) have been analyzed. Both the pictorial and the numerical results of electron density and PDF studies show mixed ionic and covalent characters in PbTe.     

Zur Tiefenverteilung der durch Elektronenstoß angeregten charakteristischen Röntgenstrahlung von Bor,Kohlenstoff, Aluminium und Silber

The peak intensity of the X-ray emission bands of boron (BK; 67 Å), carbon (CK; 44 Å), aluminium (AlL _2,3; 171 Å), and silver (AgMζ; 40 Å) excited by electron bombardment of evaporated targets has been measured as a function of the thickness of the target and at several accelerating voltages in the range 1 to 4 kV. The electron beam was inclined at an angle of 50° to the surface of the target; the take-off angle for the radiation was about 20°. From these measurements one obtaines the thickness of layers effective in producing X-rays. The influence of surface contamination and oxide layers on the intensity distribution of emission bands is discussed. It is then shown that the effect of anode self-absorption can be evaluated, if the absorption coefficientμ(λ) is available. As an example theL ₃/L ₂ intensity ratio of aluminium, and an averaged depth of X-ray production are calculated; moreover data for the electron range are given and compared with earlier results. Finally the BK-emission band of evaporated boron is presented.     

Molecular dynamics simulation studies of cryoprotective agent solutions: the relation between melting temperature and the ratio of hydrogen bonding acceptor to donor number

Molecular dynamics simulations have been carried out for glycerol–water–sodium chloride ternary solution due to its important role in cryopreservation engineering. The radial distribution functions for atom pairs potentially related to C–H ··· O and O–H ··· O hydrogen bonds were calculated. The radial distribution functions for the H (connected to C)–O atom pair do not exhibit peaks between 2 and 3 Å, whereas the radial distribution functions for the C–O atom pair exhibit distinct peaks between 3 and 4 Å. The reason for this is because most C–H ··· O geometries are bent and deviate from linearity. The ratios of acceptor to donor numbers for water and glycerol molecules decrease as the solute concentration increases. A characteristic concentration has been found that divides solutions with different mechanisms. Below the characteristic concentration, the melting temperature is linearly related to the ratio of acceptor to donor number for water molecules, whereas above the characteristic concentration, the melting temperature is linearly related to the ratio of acceptor to donor number for glycerol molecules. Further studies indicate that the relations are independent of hydrogen bonding criteria and temperature.