Microwave spectrum and structure of furfural

The microwave spectrum of furfural was investigated in the frequency range 7 GHz-21 GHz and 49 GHz-330 GHz. The ground and first torsional state of trans-furfural and ground state of cis-furfural were assigned and analyzed. A total of 1720 rotational lines with J up to 100 and K_a up to 53 were assigned to the ground state of trans-furfural, 1406 rotational lines with J up to 100 and K_a up to 48 were assigned to the first torsional state of trans-furfural and 2103 rotational lines with J up to 90 and K_a up to 48 to the ground state of cis-furfural. Accurate sets of centrifugal distortion constants for both conformations have been determined for the first time. The spectra of all ¹³C and ¹⁸O singly substituted isotopic species were observed in natural abundance in the 7 GHz-21 GHz range. Molecular structure co-ordinates, bond lengths and angles of the Kraitchman substitution type (r_s) and pseudo-Kraitchman type (r_pKr) are derived from the isotopic studies.     

Quasiparticle band structure and optical spectrum of LiBr

The electronic structures of the Fe-doped perovskite ruthenates BaRu_1?x Fe _x O₃ with x = 0, 0.25, 0.5, 0.625, 0.75, and 1 are investigated through density-functional calculations. Large exchange splitting and small crystal field splitting are found in BaFeO₃, and a contrary scenario can take place on BaRuO₃ as expected since the Ru atom has a highly extended 4d orbital. The small exchange splitting and extended 4d states are the reasons why the obtained spin magnetic moment (0.628μ _B ) is significantly lower than the spin only value (2μ _B ) for the t _2g 3↑ t _2g 1↓ electronic configuration for Ru⁴⁺ ion. Further investigations suggest that Fe substitution at the Ru sites can suppress the bandwidths of Ru 4d orbital, leading to the half-metallic behaviour in BaRu_1?x Fe _x O₃ with x = 0.625 and 0.75. The different orbital feature of the Ru⁴⁺ ions in BaRu_0.375Fe_0.625O₃ is presented, which reflects the influence of Fe dopant on Ru 4d orbitals.     

Electronic structure of MnSb

On the basis of a two center tight binding model the recursion method of Haydock et al. was applied to calculate spin polarized and non-polarized electronic densities of states and magnetic moments for the B8₁ crystal structure and a fictitious B32 structure of MnSb. The model implies the itinerant nature of the Mn d-states hybridizing with Sb p-states. For the non-polarized densities of states the self-consistent charge transfer amounts to 0.6 electrons from Mn to Sb with a band center difference of E_p ? E_d = - 0.75 eV. For the magnetic moments, which were also calculated self-consistently, 3.5 μ_B for the d-band and 3.34 μ_B in total were obtained for the B8₁ crystal structure. For the B31 structure bigger moments of 3.67 μ_B and 3.53 μ_B were obtained, correspondingly. The results for MnSb are also discussed with respect to very recent results for MnAs calculated within the same model. The local densities of states as obtained for MnSb are in good agreement with experimental XPS results.     

Electronic structure of dichalcogenide and dipnictide anions

The Self-Consistent-Field Xα Scattered Wave Cluster MO method is used to calculate molecular orbital energy level diagrams for O₂, O₂^?, O₂^2?, S₂, S₂^2?, Se₂^2?, P₂^4?, As₂^4? and AsS^3?. Calculated energies are in good agreement with those measured by photoemission spectroscopy for O₂, S₂, S₂^2? in ZrS₃, Se₂^2? in ZrSe₃ and P₂^4? in TiP₂. For O₂^? the calculated energy of the π_u → π_g transition agrees fairly well with that of the UV absorption observed in LiO₂. The predicted photoemission spectrum of O₂^2? is consistent with a preliminary study on BaO₂. Calculated valence region widths in peroxides are found to be significantly greater than the calculated oxygen atomic valence _s-p separation while valence widths for the other anions closely match atomic valence s-p splittings. This effect arises from the instability of the peroxide antibonding orbitals which correlates with the absence of dsun peroxides and Superoxides. Calculations on a Cin2v geometry FeO₆su9? cluster show that the difference in energy of O2p nonbonding and Fe3d crystal field type orbitals drops sharply as an O-O edge is contracted, providing a mechanism for Fe³⁺ → Fe²⁺ reduction at high pressure.     

Microwave spectrum and molecular structure of bromoacetonitrile

The ground state microwave spectrum of BrCH₂CN has been observed and assigned in the P- and R-band regions. For two isotopic species a series of strong Q-branch transitions, several clusters of μ_a-typeR-branch transitions and scattered μ_b-type and R- and P-branch transitions were fit using both the rigid rotor approximation and the reduced hamiltonian of Watson. The hyperfine structure due to the bromine atom has been analyzed and the complete field gradient tensor determined. A least-squares structure consistent with the observed rotational constants has been determined, has been shown to exhibit internal consistency and has been found to be in agreement with the structures of similar molecules.     

Aluminium based amorphous and nanocrystalline structure

Aluminium based rapidly quenched alloys of nominal composition Al₉₀Fe₇Nb₃ and Al₉₄Fe₂V₄ were studied by Mössbauer spectroscopy. Samples annealed up to 573 K showed amorphous structure represented by quadrupole doublet. From corrected spectra areas the values of f-factor were calculated. In the case of AlFeNb samples f-factor was estimated as f = 0.26 and for AlFeV f = 0.31. The corresponding Debye temperatures were also calculated. Higher temperature annealing at 773 and 873 K induced deformation of nano- and microcrystalline state. Mössbauer spectra of samples of both compositions (with vanadium as well as with niobium) annealed at 773 K showed superposition of crystalline phases with dominant role of Al₃Fe alloy. During annealing at 873 K, phases with large grains and small amount of FeAl metastable phase were developed (Das et al. Mat. Sci. Eng., A304–A306, 159, 2001; Illeková et al. Mat. Sci. Eng., A375–A377, 946, 2004).     

Anharmonic potential function and equilibrium structure of methane

The vibration-rotation constants of methane-d₂ reported by Deroche [Ph.D. Thesis, Paris (1977)] were analyzed by a method of Hoy et al. [Mol. Phys. 24, 1265–1290 (1972)]. All the observed α constants were well reproduced by using 13 third-order anharmonic potential constants except for α₇^A and α₄^A; the discrepancies were ascribed to a large Coriolis interaction between ν₄ and ν₇. Of the 13 third-order potential constants thus derived only f¹¹¹ (1 means one of the CH stretching coordinates) was significant and others were determined either with large uncertainties or not uniquely because of redundancy. The observed rotational constants in the ground state were corrected for the centrifugal distortion effects, the electron “slipping” effects, and the contributions from the zero-point vibrations, to derive the equilibrium rotational constants. The r_e(CH) length thus obtained is 1.087₀ ± 0.0007 Å. This result was compared with those from an ab initio calculation and from recent electron-diffraction experiments.     

Size analysis and magnetic structure of nickel nanoparticles

The size distribution of an assembly of fcc nickel nanoparticles is studied by measuring the temperature dependent magnetization curves fitted by a uniform model and a core-shell model, both based on the Langevin function for superparamagnetism with a log-normal particle volume distribution. The uniform model fits lead to a spontaneous magnetization M_s much smaller than the M_s for bulk nickel and to particle sizes larger than the ones evaluated by transmission electron microscopy; the core-shell model fits can result in a correct size distribution but the M_s in the core becomes significantly greater than the M_s for bulk nickel. It is concluded that there is a core-shell magnetic structure in nickel particles. Although the enhanced M_s in the core may be related to the narrowing of the energy bands of 3d electrons in small fcc nickel particles, the modeling values of M_s are over large compared with previous calculations on nickel clusters of different structures, which implies possible existence of an exchange interaction between the core and the shell, which is not considered in the simple core-shell model.     

The microwave spectrum and structure of chloromethyl cyclopropane

The microwave spectra of $\text{CH}{}_2\text{CH}{}_2\text{CH}$CH₂³⁵Cl and $\text{CH}{}_2\text{CH}{}_2\text{CH}$CH₂³⁷Cl have been observed and lines assigned to the gauche form. The rotational constants in MHz and distortion constants in KHz are: C₃H₅CH₂³⁵Cl, A = 11745.65, B = 2047.274, C = 1886.622, Δ_J = 0.85, Δ_JK = ? 0.9, Δ_K = 44., δ_J = ? 0.099, δ_K = 19.1, C₃H₅CH₂³⁷Cl, A = 11691.61B = 1997.664, C = 1842.823, Δ_J = 0.7, Δ_JK = ? 64.6, Δ_K = 2400, δ_J = 0.19, δ_K = ? 67.     

Synthesis,structure, and properties of BIFENBVOX

Solid solutions Bi₄V_2-x Fe _x/2Nb _x/2O_11-δ (х?=?0.05–1.0) and Bi₄V_2-х-y Fe _x Nb _y O_11–δ (with fixed x or y?=?0.2 and variable х or y?=?0.2–0.5 with step 0.1) were synthesized by the standard ceramic technology in the temperature range 773–1113 K and by mechanochemical activation method using Bi₂O₃, V₂O₅ Fe₂O₃, and Nb₂O₅ oxides as initial compounds. The formation of solid solutions was studied. Ranges of stability and temperature values of phase transitions for different polymorphous modifications were defined using dylatometric and thermo gravimetric studies. The morphology and the local chemical composition of the ceramic samples were studied. Samples with concentration of dopants x?>?0.3 contain two phases; both major and impurity phases are solid solutions of the BIFENBVOX type although the dopants atoms distribution between them is random. The thermal expansion coefficients (TEC) were measured. The electrical conductivity of ceramic samples was investigated in a wide range of temperatures. The highest conductivity values among the studied solid solutions are observed for the sample with a small amount of dopants x?=?0.25.     

Spectral methods and cluster structure in correlation-based networks

We investigate how in complex systems the eigenpairs of the matrices derived from the correlations of multichannel observations reflect the cluster structure of the underlying networks. For this we use daily return data from the NYSE and focus specifically on the spectral properties of weight W_ij=|C|_ij−δ_ij and diffusion matrices D_ij=W_ij/s_j−δ_ij, where C_ij is the correlation matrix and s_i=∑_jW_ij the strength of node j. The eigenvalues (and corresponding eigenvectors) of the weight matrix are ranked in descending order. As in the earlier observations, the first eigenvector stands for a measure of the market correlations. Its components are, to first approximation, equal to the strengths of the nodes and there is a second order, roughly linear, correction. The high ranking eigenvectors, excluding the highest ranking one, are usually assigned to market sectors and industrial branches. Our study shows that both for weight and diffusion matrices the eigenpair analysis is not capable of easily deducing the cluster structure of the network without a priori knowledge. In addition we have studied the clustering of stocks using the asset graph approach with and without spectrum based noise filtering. It turns out that asset graphs are quite insensitive to noise and there is no sharp percolation transition as a function of the ratio of bonds included, thus no natural threshold value for that ratio seems to exist. We suggest that these observations can be of use for other correlation based networks as well.     

The relation between crystal structure and luminescence in β-alumina and magnetoplumbite phases

Crystallographic data of aluminate and gallate β-aluminas and magnetoplumbites are reviewed. For the XAl₁₁O₁₇ and XGa₁₁O₁₇ compounds c/a increases with increasing r_X+. The magnetoplumbites have c/a values ranging between 3.915 and 3.954 with the exception of BaAl₁₂O₁₉ and BaGa₁₂O₁₉. These compounds seem to have strongly distorted magnetoplumbite-derived structures. Upon activation of the MeAl₁₂O₁₉(Me = Ca, SrorBa) lattices with Eu²⁺ and Ce³⁺, the luminescence properties of Ba containing compounds deviate from the other compounds. This seems to be due to different co-ordinations of the activator ions. Substitution of Mg²⁺ for Al³⁺ in magnetoplumbite phases results in the case of SrAl₂O₁₉ in changes of the c/a ratio, of diffraction intensities and of the luminescence properties. The various data suggest a close similarity of this type of phases and BaAl₁₂O₁₉. In the MeGa₁₂O₁₉ series (Me = SrorBa), the quantum efficiency of BaGa₁₂O₁₉: Mn²⁺ was found to be anomalously low.     

Magnetic structure and crystal field in cerium compounds with CsCl-type structure

Neutron diffraction and spectroscopy experiments have been performed on the cubic (CsCl-type structure) compounds CeAg, CeZn and CeMg. CeAg orders ferromagnetically with a moment μ_F= 0.8μ_B at 1.7 K. CeZn and CeMg are antiferromagnets; at 4.2 K their magnetic moments are 1.95 μ_B (CeZn) and 1.85 μ_B (CeMg). In the ordered state, they reveal a strong quadratic distortion, the (c/a ? 1) value reaching 1.9% in CeAg at 1.7 K; in CeAg additional atoms shifts seem to be present in the tetragonal cell. Crystal field parameters have been determined as |A₄ 〈r₄〉| = 117 K (CeAg), 74 K (CeZn) and 117 K (CeMg); the consistence of the results with all the previous studies is discussed.     

LFN and LSCFN perovskites — structure and transport properties

Structural, electronic and transport properties of LFN (LaFe_1−zNi_zO₃) and LSCFN (La_1−xSr_xCo_1−y −zFe_yNi_zO₃) perovskites synthesized by a modified citric acid method were studied. Structure of the samples was characterized by X-ray studies with Rietveld method analysis. Magnetic properties and valence states of iron ions were characterized by ⁵⁷Fe Moessbauer spectroscopy performed at RT, which were found to be greatly dependent on the chemical composition of the samples. Electrical conductivity was measured in the 20–800 °C temperature range and for some compositions relatively high values (exceeding 100 S cm^− 1) were observed in the 600–800 °C range. Chemical stability studies in relation to Ce_0.8Gd_0.2O_1.9 electrolyte, performed for selected perovskite samples, revealed decreasing stability with increasing Ni concentration and formation of solid solutions in CGO/perovskite composites. The coefficient of thermal expansion (CTE) of LFN perovskites was found to match that of CGO electrolyte (CTE in the 10–13 · 10^− 6 K^− 1 range).     

First principle electronic structure calculations of ternary alloys Hg1−xMnxTe in zinc-blende structure

We have investigated the structural, electronic, magnetic and optical properties of Hg_1?xMn_xTe in the zinc-blende phase for 0≤x≤1. The calculations were performed by using the full potential linearized augmented plane wave plus local orbitals method within the framework of the density functional theory. The lattice constants of Hg_1?xMn_xTe at different Mn concentrations exhibit Vegard's law perfectly. For spin-up channel the Mn 3d bands are occupied and mixed with the Te 5p bands whereas for spin-down channel the Mn 3d bands are unoccupied. The values of the p–d exchange splitting energy, ?_x(pd) as produced by the Mn 3d states are given. The contribution of the valence band and the conduction band in the process of exchange and splitting is described by the exchange coupling constants N₀α and N₀β. Due to p–d hybridization the magnetic moment of the Mn atom reduces, which results in small local magnetic moments on the non-magnetic Hg and Te sites. The potential applications of Hg_1?xMn_xTe in infrared device have been discussed on the basis of its optical properties.     

Hyperfine structure in hydrogen and helium ion

QED theory of the hyperfine splitting of the 1s and 2s state in hydrogen isotopes and helium-3 ion is considered. We develop an accurate theory of a specific difference 8E_HFS(2s)−E_HFS(1s). We take into account higher-order QED and nuclear structure effects. In particular, we found the vacuum polarization contribution in order α(Zα)³E_F and examined the recoil contribution in order (Zα)³m/M and thus completed a calculation of the fourth order QED corrections. The higher-order nuclear structure contributions were also analysed. The theoretical predictions reported here are now of a higher accuracy than the experiment. The study of the difference provides the most accurate test (at a level of a part in 10⁸) of the QED theory of ns HFS up to date. The theory agrees with most of the experimental data.     

The charge structure and interaction mechanism on In-doped sulphur spinel

The charge structure and interaction mechanism on In-doped sulphur spinel FeIn_xCr_2−xS₄ are studied. The temperature dependence of magnetization μ_B, measured from 60 K to room temperature, suggests that FeIn_xCr_2−xS₄ (x=0.1$x=0.1$, 0.3) are ferrimagnetic. The Néel temperature is decreased with increasing non-magnetic In substitution as consequence of reduction of superexchange interaction for increased lattice parameter. FeIn_xCr_2−xS₄ is investigated by Mössbauer spectra from 4.2 K to room temperature. The asymmetric line broadening is observed for the sample FeIn_xCr_2−xS₄ and considered to be dynamic Jahn–Teller relaxation. The charge state of Fe ions is ferrous in character.     

Hyperfine structure and nuclear moments of99Ru and101Ru

The atomic-beam magnetic-resonance method in combination with the triple resonance technique has been used to determine the nuclear magnetic dipole moments of⁹⁹Ru and¹⁰¹Ru. The moments are deduced fromrf transition measurements in the⁵F₅ and⁵F₄ states at magnetic fields between 770 and 2400 Oe. In order to reduce the part of the uncertainty of the moments which arises from the uncertainty of the hyperfine structure constants more precise values of the constants than those available up to now were determined from low field measurements. After making corrections for hyperfine and Zeeman interactions with neighbouring atomic states we obtain the following values for the magnetic dipole moments:μ ₉₉=?0.6381 (51)μ _N andμ ₁₀₁=?0.7152 (60)μ _N (uncorrected for diamagnetic shielding). The results of the present work combined with the results of an earlier hyperfine structure investigation in the⁵F multiplet are analysed with respect to the effective-operator formalism. From this analysis we obtain the following values for the electric quadrupole moments:Q ₉₉=0.076 (7) b andQ ₁₀₁=0.44 (4) b (uncorrected for Sternheimer shielding or antishielding).     

Magnetic and crystal structure of copper(II) fluoride

A powder sample of the monoclinic, weak ferromagnet CuF₂ was investigated by neutron diffraction. Using the profile method, the crystal structure was refined and the spin configuration determined. The layer type structure with planar quadratic fluorine coordination of Cu²⁺ (3d⁹) and the magnetic structure are remarkably similar to those of AgF₂. The spin configuration is however different from the magnetic structures of other 3d-fluorides; the magnetic unit cell is doubled with respect to the chemical cell (a_m = 2a, P2₁/c). The ordered magnetic saturation moment corresponds to quenched orbital momentum.     

Studies in molecular structure,symmetry and conformation—Part XIV. Crystal and molecular structure of L-isoleucine hydrochloride monohydrate form II

The crystal structure of a new form of L-isoleucine hydrochloride monohydrate C₆H₁₃O₂NHClH₂O (termed form II) has been determined using three-dimensional photographic data. This differs conformationally from the hydrochloride derivative (termed form I, Trommel and Bijvoet 1954) reported earlier. The crystal belongs to the orthorhombic space group P2₁2₁2₁ with cell dimensions,a=5.87±0.01,b=24.77±0.02 andc=6.85±0.01 ? and four molecules per cell,ρ _obs=1.240 g/cm³,ρ _cal=1.238 g/cm³,μ for CuKa=32.6 cm⁻¹. Contribution No. 420 from the Department of Crystallography and Biophysics, University of Madras, Madras 600025.