NMR study of the electric field gradient in the paramagnetic phase of M<Subscript>3</Subscript>V<Subscript>2</Subscript>O<Subscript>8</Subscript> (M = Co,Ni) compounds

The NMR spectra and the decay of a spin echo signal from ⁵¹V nuclei in Kagome-staircase Co₃V₂O₈ (CVO) and Ni₃V₂O₈ (NVO) single crystals are measured in the temperature range 30–300 K and a magnetic field H ₀ = 20 kOe. The orientation dependences of the ⁵¹V NMR line shape are used to determine the electric field gradient (EFG) parameters, namely, quadrupole frequency ν _Q and asymmetry parameter η. These parameters for NVO and CVO are ν _Q = 180(10) kHz, η = 0.5(1) and ν _Q = 130(10) kHz, η = 0.6(1), respectively. A comparison of the results of calculating EFG tensors with a point charge model and the NMR data indicates that the crystallographically equivalent vanadium atoms in the Ni₃V₂O₈ and Co₃V₂O₈ compounds differ in the EFG axis orientation. M₃V₂O₈ crystals are found to have vanadium positions (V1, V2) with different orientations of the z axis, which specifies the direction of the principal value of EFG (V _zz ): these orientations lie in the bc plane and make an angle of either +51(5)° (V1) or −51(5)° (V2) with axis c. In the temperature range 30–300 K, the EFG tensor components and the local symmetry of the charge surrounding of the vanadium positions in NVO and CVO oxides are found to change insignificantly.     

Electric field gradient in bixbyite rare-earth oxides R2O3 (R=Tl,Eu, Lu,Tm) measured by perturbed angular correlation

The electric field gradient (EFG) at ¹¹¹Cd nuclei dilutely substituting the cation site in bixbyite rare-earth oxides Tl₂O₃, Eu₂O₃, Lu₂O₃ and Tm₂O₃ has been measured using perturbed angular correlation technique. The ¹¹¹In(EC) ¹¹¹Cd probe nuclei were introduced into the samples by thermal diffusion. The experimental EFG values are compared with those calculated using the point charge model (PCM). The results are discussed in terms of a correlation between the electric field gradient and cation–oxygen bond length in metal oxides. This revised version was published online in August 2006 with corrections to the Cover Date.     

A CEMS study of ac-axis oriented thin film of YBa2(Cu0.97 57Fe0.03)3O7

⁵⁷Fe Mössbauer spectra of a fullyc-axis oriented epitaxial thin film of YBa₂(Cu_0.97 ⁵⁷Fe_0.03)₃O₇, recorded by CEMS, are reported. Spectra taken at different angles between the normal of the film (i.e. thec-axis) and the gamma ray direction show that for two of the three observed quadrupole doublets the main component of the EFG lies in thea?b-plane, for the third doublet it is parallel to thec-axis. The EFG of all three doublets has approximately axial symmetry.     

A Theoretical Study of <Superscript>51</Superscript>V Electric Field Gradient Tensors in Pyrovanadates and Metavanadates

A computational study of the ⁵¹V electric field gradient (EFG) tensors in pyrovanadates, α-Zn₂V₂O₇, Cd₂V₂O₇, β-Mg₂V₂O₇ and BaCaV₂O₇, and the metavanadates, LiVO₃, α-NaVO₃, KVO₃, ZnV₂O₆ and MgV₂O₆, is presented. Restricted Hartree–Fock and hybrid density functional theory calculations have been used to investigate the effects of the size of vanadium-oxygen clusters, basis set size, proton-termination and embedded cluster techniques on the accuracy of the calculated EFG tensors. Good agreement between theory and experiment is obtained for most of the vanadates. A sound methodology is suggested for calculating the EFG tensor in pyrovanadates which contain isolated V₂O₇ ⁴⁻ clusters. For metavanadates, the charges of the bridging oxygen atoms can be differentiated from those of terminal oxygen atoms by terminating the former with hydrogen atoms, and embedded cluster molecular orbital calculations are useful in accounting for the long-range electrostatic interactions which influence the EFG tensor components. EFG tensor orientations vary for different pyrovanadate structural types, and individual components are confined by symmetry elements in the metavanadates. A preliminary comparison is made between ⁵¹V EFG tensors calculated with ab initio and plane wave methods. Theoretical EFG tensor components and orientations, in combination with experimental ⁵¹V solid-state nuclear magnetic resonance data, are demonstrated to be useful tools for prediction of molecular structure. Authors' address: Robert W. Schurko, Department of Chemistry and Biochemistry, University of Windsor, Windsor, Ontario N9B 3P4, Canada     

NMR spectra of57Fe in hexagonal ferrites with magnetoplumbite structure

The NMR spectra of⁵⁷Fe in domains of MFe₁₂O₁₉ (M=Ba, Sr, Pb) were measured by spin echo technique at 4.2 K. The change of the heavy ion causes frequency shifts of lines corresponding to Fe³⁺ ions in 2b and 4f₂ sites while leaving other lines essentially unchanged; the significant role of different Fe³⁺−M²⁺ bonding was found. The dipolar broadening of lines in BaFe₁₂O₁₉ caused by random and static displacement of bipyramidal Fe³⁺ ions from the mirror plane is calculated and the results are compared with the experiment.     

Determination of the orientation of the electric field gradient at the Cu(1) site from the Mössbauer spectra of textured pellets made of YBa2Cu3O7−δ superconductor

A textured pellet of YBa₂Cu₃O_7?δ was prepared and doped with⁵⁷Co. After subsequent heat treatments the cobalt was found at the two copper sites. The degree of alignment of individual crystallites (about 40%) was determined from the Mössbauer spectrum by using a method developed by the authors [1]. The same method showed that the most characteristic doublet component of such spectra (δ=0.08 mm/s; |ΔE _Q|=1.96 mm/s) is associated with a site, most probably a Cu(1) site, where the EFG is parallel to thec direction of the unit cell. The sign ofV _zz turned out to be negative, giving a negative quadrupole splitting (ΔE _Q=?1.96 mm/s) for that component.     

NQR indications of unconventional magnetism in some bismuth-based diamagnets

An evidence that local ordered magnetic fields from 30 to 200 G exist in diamagnets α-Bi₂O₃, Bi₃O₄Br, Bi₄Ge₃O₁₂, Bi₂Al₄O₉ which comprise neither d- nor f-elements was earlier given by the zerofield and Zeeman-perturbed²⁰⁹Bi nuclear quadrupole resonance (NQR) spectra. With a view to find similar spectroscopic effects in other compounds, we examined the²⁰⁹Bi NQR Zeeman-perturbed spectra of the Bi₃B₅O₁₂ oriented single crystal as well as the zero-field spin echo envelopes in Bi₃B₅O₁₂ and Bi₂Ge₃O₉. Distinctive modulations were displayed by the zero-field²⁰⁹Bi spin echo envelopes in Bi₂Ge₃O₉ powder. The modeling of the spin echo envelopes within the density matrix formalism explained the observed effect by the presence of local ordered magnetic field of the order of 65 G at the Bi atoms. The zero-field modulations of the²⁰⁹Bi spin echo envelopes were also observed in Bi₃B₅O₁₂ indicating the presence of the internal source of line splitting. This finding and considerable deviation of the resonance intensity ratios from that in a pure NQR, found in the zero-field²⁰⁹Bi spectrum of the single crystal, were understood as indirect evidences that a local ordered magnetic field exists also in Bi₃B₅O₁₂. The zero-field²⁰⁹Bi spin echo envelopes assigned to the lines split by the local magnetic fields in α-Bi₂O₃ and Bi₄Ge₃O₁₂ were observed to display modulations on the appropriate curves.     

Theoretical studies of the optical and EPR spectra for V in Y2O3 crystal

In this paper, we give an alternative suggestion that both the observed optical and electron paramagnetic resonance (EPR) spectra of Yttrium oxide (Y₂O₃):V³⁺ are attributed to V³⁺ ions at the S₆ site of Y₂O₃. This suggestion is different from the opinion in the previous paper that the optical and EPR spectra are attributed to V³⁺ ions at the C₂ and S₆ sites, respectively. From the suggestion, the optical band positions and spin-Hamiltonian parameters are calculated by diagonalizing the complete energy matrix for 3d² ions in trigonal symmetry. The results are in good agreement with the experimental values, suggesting that both the observed optical and EPR spectra in Y₂O₃:V³⁺ may be due to V³⁺ at S₆ site of Y₂O₃ crystal.     

Ab initio study of the EFG tensor at Cd impurities in Sc2O3 semiconductor

We present an ab initio study of diluted Cd impurities localized at both cation sites of the semiconductor Sc₂O₃. The electric-field-gradient (EFG) tensor at Cd impurities located at both cationic sites of the host structure was determined from the calculation of the electronic structure of the doped system. Calculations were performed with the full-potential augmented-plane wave plus local orbitals (APW+lo) method within the framework of the density functional theory. We studied the atomic structural relaxations and the perturbation of the electronic charge density induced by the impurities in the host system in a fully self-consistent way. We showed that the Cd impurity introduces an increase of 8% in the nearest oxygen neighbors bond-lengths, changing the EFG sign for probes located at the asymmetric cation site. The APW+lo predictions for the charged state of the Cd impurity were compared with EFG results existent in the literature, coming from time-differential γ–γ perturbed-angular-correlations experiments performed on ¹¹¹Cd-implanted Sc₂O₃ powder samples. From the excellent agreement between theory and experiment, we can strongly suggest that the Cd acceptor impurities are ionized at room temperature. Finally, we showed that simple calculations like those performed within the point-charge model with antishielding factors do not correctly describe the problem of a Cd impurity in Sc₂O₃.     

Cr4+在Al2O3多晶体中的光谱性能研究

采用传统无压烧结工艺制备Cr:Al₂O₃透明多晶陶瓷.测定了其退火前后的吸收光谱和荧光光谱，发现在Al₂O₃六配位的八面体结构中，Cr⁴⁺的荧光发射也处在1100—1600nm波段的红外区间，荧光发射峰位于1223nm附近，类似Cr⁴⁺在四面体中的发光行为.同时由于氧化铝晶格常数较小，晶体场强较强，使Cr⁴⁺:Al₂O_{3< 关键词： 4+')" href="#">Cr⁴⁺ 2}O₃透明陶瓷')" href="#">Cr:Al₂O₃透明陶瓷 光谱性质 八面体     

Electric field gradients in PrBa2 Cu 3 O 7 : LSDA+U results and comparison with experiment

Electric-field gradient (EFG) and asymmetry parameter (η) at all oxygen and copper sites of nonsuperconducting PrBa₂Cu₃O₇ (Pr123) compound were calculated using the full-potential (linearized)-augmented-plane-wave plus local orbitals method. Exchange and correlation effects were treated by LSDA+U for Cu(3d) and Pr(4f) electrons. The effects of changing screened Coulomb parameters U_Pr, U_Cu1, and U_Cu2 on the results were individually studied. The calculated EFG of O2 site is close to the EFG of O3 site at variance with the experimental result. It was shown that by increasing superconducting holes in O2 and O3 sites the EFG at these sites increase and vice versa. The most famous theories which have been proposed to explain the suppression of superconductivity in perfect (without any mis-substitution or other defects) Pr123 compound are not consistent with the experimental EFG at O2 and O3 sites. By replacing one Pr atom at the Ba site on unit cell of Pr123 (Pr_Ba), it was shown that Pr_Ba mis-substitution reduces the superconducting holes in both O2 and O3 sites and could be responsible for the suppuration of superconductivity in Pr123 samples. It is very probable that the unusual behaviors of experimental EFG at O2 and O3 sites of Pr123 are related to oxygen defects which are produced with Pr_Ba mis-substitution.     

Measurements of the electric field gradient at cadmium in the high Tc superconductor YBa2Cu3O6+x

The electric field gradient (EFG) at¹¹¹Cd probe atoms in YBa₂Cu₃O_6+x has been studied by the perturbed angular correlation (PAC) spectroscopy. After annealing at temperatures below 1000 K the probe atoms are located at the Cu(1) site; above 1100 K they preferentially occupy the Y site, whereas in the intermediate temperature range they also reside on the Ba site. A reduction of the oxygen content from x=1.0 to 0.2 resulted in a decrease of the asymmetry parameter measured at the Ba site, but in an increase of it at the Y site, indicating there a local distortion of the YBa₂Cu₃O_6+x lattice by the Cd impurity. Two different surroundings for the Cd atoms at the Cu(1) site were observed.     

Bulk magnetization and 1H NMR spectra of magnetically heterogeneous model systems

Bulk magnetization and ¹H static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of two magnetically heterogeneous model systems based on laponite (LAP) layered silicate or polystyrene (PS) with low and high proton concentration, respectively, and ferrimagnetic Fe₂O₃ nano- or micro-particles have been studied. In LAP+Fe₂O₃, a major contribution to the NMR signal broadening is due to the dipolar coupling between the magnetic moments of protons and magnetic particles. In PS+Fe₂O₃, due to the higher proton concentration in polystyrene and stronger proton–proton dipolar coupling, an additional broadening is observed, i.e. ¹H MAS NMR spectra of magnetically heterogeneous systems are sensitive to both proton–magnetic particles and proton–proton dipolar couplings. An increase of the volume magnetization by ～1 emu/cm³ affects the ¹H NMR signal width in a way that is similar to an increase of the proton concentration by ～2×10²²/cm³. ¹H MAS NMR spectra, along with bulk magnetization measurements, allow the accurate determination of the hydrogen concentration in magnetically heterogeneous systems.     

Site occupation of indium and jump frequencies of cadmium in FeGa<Subscript><Emphasis Type="Bold">3</Emphasis></Subscript>

Perturbed angular correlation (PAC) measurements using the In-111 probe were carried out on FeGa₃ as part of a broader investigation of indium site occupation and cadmium diffusion in intermetallic compounds. One PAC signal was observed with hyperfine parameters ω ₁= 513.8(1) Mrad/s and η= 0.939(2) at room temperature. By comparison with quadrupole frequencies observed in PAC measurements on isostructural RuIn₃, it was determined that indium occupies only the 8j site in the FeGa₃ structure, denoted Ga(2) below because two out of the three Ga sites have this point symmetry. PAC spectra at elevated temperature exhibited damping characteristic of electric field gradients (EFGs) that fluctuate as Cd probes jump among Ga(2) sites within the lifetime of the excited PAC level. A stochastic model for the EFG fluctuations based on four conceivable, single-step jump-pathways connecting one Ga(2) site to neighboring Ga(2) sites was developed and used to fit PAC spectra. The four pathways lead to two observable EFG reorientation rates, and these reorientation rates were found to be strongly dependent on EFG orientation. Calculations using density functional theory were used to reduce the number of unknowns in the model with respect to EFG orientation. This made it possible to determine with reasonable precision the total jump rate of Cd among Ga(2) sites that correspond to a change in mirror plane orientation of site-symmetry. This total jump rate was found to be thermally activated with an activation enthalpy of 1.8 ±0.1 eV.     

Two-dimensional spin freezing in Y1−z Ca z Ba2Cu3−x Fe x O7

Hyperfine electric and magnetic interactions in Y_1?z Ca _z Ba₂Cu_3?x Fe _x O_6+y compounds have been studied for different rates of Fe and Ca substitution (x=0.09 and 0.24;z=0.24;y=0?1) by⁵⁷Fe Mössbauer spectroscopy of powder samples obtained by different thermal treatments. Calculations of the Fe³⁺ EFG tensor have been performed for different coordination polyhedra in Cu1 and Cu2 sites. Variations of the direction, amplitude and of the sign of the principal component of the EFG are reported versus the iron displacement from the ideal Cu sites inside the pyramidal and tetrahedral coordination polyhedra. Calculated ΔE _Q and η values are compared with the experimental ones. For the Cu2 site, faithfully probed in both oxygen-depleted and oxygen-saturated samples by fairly large fraction of residing iron atoms, the mutual orientations of the axes of the principal EFG component and that of easiest magnetization are deduced from interrelations between quadrupole parameters for paramagnetic quadrupolar and magnetic Zeeman Mössbauer spectra. In the desoxygenated samples, the coexistence of a long range 2D antiferromagnetic order and of a spin-glass order has been evidenced. For the oxygen-saturated samples, the two-dimensional spin-glass order is observed belowT _f =10 K. The Mössbauer spectra under applied fields at 4.2 K show an easy polarization of the spins in the Cu2 sites.     

On Hahn-echo measurements of short 29Si T2 times in some silica-based materials

The Hahn-echo ²⁹Si NMR experiments performed for determinations of T₂ times in static supermicroporous materials SiO₂–Al₂O₃–MnO and SiO₂–MnO have shown the large loss in the echo intensity, observed at shortest echo delays. The relaxation patterns “intensity—τ”, where the echo-intensity initially increases with increasing τ values and then it “normally” reduces due to spin–spin relaxation, are formally treated and discussed.     

Mössbauer study of Cd0.1Ni0.9Sn y Fe2−2y O4 ferrites

Mössbauer spectra of Cd_0.1Ni_0.9Sn_yFe_2?2yO₄ (y=0.0 to 0.5) ferrite system have been studied. The spectra suggest the existence of two hyperfine fields, one due to Fe³⁺ tetrahedral (A) site ions and the other due to Fe³⁺ octahedral (B) site ions. The variation of isomer shift, quadrupole interaction and internal magnetic fields of⁵⁷Fe³⁺ ions in both A and B sites have been determined as function of tin concentration. The systematic decrease in Curie temperature observed in the above system with tin concentration is explained on the basis of exchange interaction.     

Calculation of EFGs in high Tc superconductors

The electric field gradients (EFGs) at all atomic positions of YBa₂Cu₃O₇ and YBa₂Cu₃O₆ are calculated on the basis of full potential linearized augmented plane wave calculations by an ab initio method. Cood agreement with experimental EFG_s is found for all oxygen positions in YBa₂Cu₃O₇ and the Cu1 position in both compounds, while for the Cu2 position in the superconductor the symmetry of the EFG agrees with experiment but the magnitude of our theoretical EFG is only half the experimental value. A small transfer of 0.07 electrons from d(x²−y²) to d(z²) symmetry would be sufficient to achleve agreement with experiment. Thus the underlying local density approximation is not perfect, but remains a very accurate method for describing ground state properties.     

Electric-field gradients at Ta donor impurities in Cr2O3(Ta) semiconductor

We report perturbed-angular-correlation (PAC) experiments on ¹⁸¹Hf(→¹⁸¹Ta)-implanted corundum Cr₂O₃ powder samples in order to determine the magnitude and symmetry of the electric-field gradient (EFG) tensor at Ta donor impurity sites of this semiconductor. These results are analyzed in the framework of ab initio full-potential augmented-plane wave plus local orbitals (FP−APW+lo) calculations. The results are also compared with EFG results coming from PAC experiments in isomorphous α-Al₂O₃ and α-Fe₂O₃ doped with ¹¹¹In→¹¹¹Cd and ¹⁸¹Hf→¹⁸¹Ta tracers. This combined analysis enables us to quantify the magnitude of the lattice relaxations induced by the presence of the impurity and to determine the charge state of the impurity donor level introduced by Ta in the band gap of the semiconductor.