Hyperfine field and electric quadrupole interaction of51V in YFe2 and HoFe2

Spin echo measurements were made on Y(Fe_0.99V_0.01)₂, (Y_0.97Ho_0.03) (Fe_0.99V_0.01)₂ and Ho(Fe_0.96 V_0.04)₂ compounds. The addition of Ho to YFe₂ causes a spin reorientation from <111> to <100> but this is not reflected in the⁸⁹Y or⁵¹V hyperfine fields. A well resolved⁵¹V NMR line was observed at 51.5 MHz and 60.0 MHz respectively for Y and Ho Laves compounds but with no evidence of quadrupole satellites. Small quadrupole splittings ¦2P_t¦ = 171 ±5 kHz and 178 ±5 kHz respectively for Y and Ho compounds were deduced from the oscillatory decay of the⁵¹V spin echo after a two pulse sequence.On leave from Department of Physics, University College, The University of New South Wales, Australian Defence Force Academy, Campbell, ACT, Australia.     

Xanes (X-ray absorption near edge structure) of V in vanadium-iron phosphate glasses

The X-ray Absorption Near-Edge Structure (XANES) of V in vanadium-iron glasses (50P₂O₅ + (50?x)FeO + xV₂O₅) have been measured. The effective charge of V ions in glasses has been determined. At low V₂O₅ concentration (x ～ 5) only V⁴⁺ with 6-fold coordination is present on the contrary a static mixed valence state (V⁴⁺, V⁵⁺) has been found at high concentrations 20?x?50. The results explain the electron hopping conductivity effects at high V₂O₅ concentration (x ～ 50) involving V⁴⁺ ? V⁵⁺ pairs and at low V₂O₅ concentration (x?10) involving V⁴⁺ ? Fe³⁺ pairs.     

NMR relaxation studies on quasi-one-dimensional conductor β-Na0.33V2O5

The spin-lattice relaxation time T₁ of ²³Na and ⁵¹V nuclei in the quasi-one-dimensional conductor β-Na_0.33V₂O₅ was measured in the temperature region between 77K and the room temperature. The large anisotropy of T₁ of ²³Na nuclei was observed. The experimental results of T₁ of ²³Na and ⁵¹V nuclei at 77K were analyzed that there exists in β-Na_0.33V₂O₅ the electron hopping motion along site I vanadium chain, of which the correlation time of this hopping motion is about 10^?12 sec.     

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.     

Microscopic magnetic properties of nonstoichiometric V2O3+x—NMR and inelastic spin-flip neutron scattering measurements

The local magnetic properties of the V sites in the nonstoichiometric V₂O_3+x (0 ? x <0.08) have been examined by nuclear magnetic resonance and inelastic spin-flip neutron scattering techniques. The samples with x = 0.01 and 0.02 show a paramagnetic metal (PM)-antiferromagnetic insulator (AFI) transition. In the AFI phase, two distinct ⁵¹V NMR signals with hyperfine fields H_n = 184.9±0.5 kOe and 71±1 kOe were observed at 1.8 K, which were assigned as due to V³⁺ and V³⁺ sites, respectively. On the other hand, the samples with x = 0.04 and 0.06 were metallic down to 1.4K, and showed a paramagnetic (PM)-antiferromagnetic (AFM) transition at about 10 K. In these samples, a ⁵¹V NMR signal with H_n = 58±2 k0e and one with 〈H_n〉 = 9kOe were observed at 1.8 K, which were assigned as due to V³⁺-like sites and the matrix V sites, respectively. These results are entirely consistent with those obtained from the neutron experiment. We propose that in the metallic phase (0.04 ? x < 0.08) the minority V⁴⁺-like sites are magnetically localized in the delocalized V matrix and may be responsible for the antiferromagnetic long range order below 10 K.     

Hyperfine interaction in the mixed conductor γ LiV2O5

Transferred hyperfine interaction effects as studied from⁵¹v NMR in LiV₂O₅ (bronze) between the non-magnetic V⁵⁺ and paramagnetic V⁴⁺ lead to differing non-integral valences (neither 5+ nor 4⁺) on these sites at room temperature and below. However, at high temperatures exchange between two sites leads to a single mixed-valence state. d-d (V⁴⁺ –V⁴⁺) pairing along with relaxation effects show up in the low temperature spectra. Though susceptibility remains almost constant from 300–100K, there is considerable narrowing as well as intensification of the lines.     

Investigation of vanadium–sodium silicate glasses using XANES spectroscopy

X-ray absorption near edge structure spectroscopy has been used to investigate the electronic and atomic structure of (V₂O₅)_x(Na₂O)_0.30(SiO₂)_0.70−x (x < 0.1) glasses obtained by melt-quench technique. The results show no sign of metallic clustering of V atoms, but mixed oxidation states (+4 and +5) of V and strong V3d–O2p hybridization in the glasses. Detailed analysis has revealed that the glass samples contain about 15% V⁴⁺ and 85% V⁵⁺ and the ligand-field splitting is about 1.6 eV.     

Measurement of50V and51V nuclear moments by nuclear magnetic resonance methods

From measurements of the Larmor frequencies of²H,⁵⁰V and⁵¹V in aqueous vanadate solution the ratio of theg _I-factors of⁵⁰V and⁵¹V and the nuclear magnetic moments of⁵⁰V and⁵¹V are derived. The ratio of the longitudinal relaxation times T₁ in VOCl₃ yields the ratio of the quadrupole moments |Q(⁵⁰V)/Q(⁵¹V)|=(3.99±0.14). In the 3d ³ 4s ^{2 4} F _3/2 atomic ground state the hyperfine structure anomaly is smaller than 1·10^?5.     

Potential-induced sonoelectrochemical graphene nanosheets with vacancies as hydrogen peroxide reduction catalysts and sensors

Defective graphene nanosheets (dGN_4V) with 5-9, 5-8-5, and point defects were synthesised by a sonoelectrochemical method, where a potential of 4 V (vs. Ag/AgCl) was applied to drive the rapid intercalation of phosphate ions between the layers of the graphite foil as a working electrode. In addition to these vacancies, double vacancy defects were also created when the applied potential was increased to 8 V (dGN_8V). The defect density of dGN_8V (2406 μm⁻²) was higher than that of dGN_4V (1786 μm⁻²). Additionally, dGN_8V and dGN_4V were applied as catalysts for the hydrogen peroxide reduction reaction (HPRR). The mass activity of dGN_8V (1.31 × 10⁻² mA·μg⁻¹) was greater than that of dGN_4V (1.17 × 10⁻² mA·μg⁻¹) because of its high electrochemical surface area (ECSA, 1250.89 m²·g⁻¹) and defect density (N_D, 2406 μm⁻²), leading to low charge transfer resistance on the electrocatalytic interface. The ECSA and N_D of dGN_4V were 502.7 m²·g⁻¹ and 1786 μm⁻², respectively. Apart from its remarkable HPRR activity, the cost-effective dGN_8V catalyst also showed potential as an amperometric sensor for the determination of H₂O₂.     

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     

Microstructural, dielectric and spectroscopic properties of Li2O-Nb2O5-ZrO2-SiO2 glass system crystallized with V2O5

Li₂O-Nb₂O₅-ZrO₂-SiO₂ glasses mixed with different concentrations of V₂O₅ were crystallized. The samples were characterized by XRD, SEM and DTA techniques. The SEM pictures indicated that the samples contain well defined and randomly distributed crystal grains. The X-ray diffraction studies have revealed the presence of several crystalline phases in these samples. Optical absorption, ESR and photoluminescence spectral studies on these samples have indicated that a considerable proportion of vanadium ions do exist in V⁴⁺ state in addition to V⁵⁺ state and the redox ratio seems to be increasing with increase in the concentration of crystallizing agent V₂O₅. The infrared spectral studies have pointed out the existence of conventional SiO₄, ZrO₄, NbO₆, VO structural units in the glass ceramic network. The study of dielectric properties suggested a decrease in the insulating character of the glass ceramics with increase in the crystallizing agent. A.C. conductivity in the high temperature region seems to be connected mainly with the polarons involved in the process of transfer from V⁴⁺↔V⁵⁺ ions.     

V替代Mn对La_(0.45)Ca_(0.55)MnO_3电荷有序相及自旋玻璃态的影响

用固相反应法制备了La0.45Ca0.55Mn1-xVxO3(x=0.00,0.10)多晶样品.通过X射线衍射谱、质量磁化强度-温度曲线、电子自旋共振谱,研究了V5+替代Mn3+/Mn4+对La0.45Ca0.55MnO3电荷有序相和自旋玻璃态的影响.实验结果表明,当x=0.10时,不仅母体的电荷有序相基本破坏,而且母体在40K左右出现的自旋玻璃态也被融化.电荷有序相被破坏的主要原因是用V5+替代Mn3+/Mn4+后,增加了Mn3+与Mn4+的比例,使铁磁双交换作用优于反铁磁超交换作用;自旋玻璃态的融化是由于V替代Mn后破坏了反铁磁背景下有少量铁磁成分的自旋玻璃态的形成条件.     

Photomagnetic effects and disaccommodation in Co-doped YIG

Y₃Fe₅O₁₂ (YIG) doped with ≦ 0.01 Co per molecule in combination with small dopes of V or (and) Mn show a decrease of the permeability in the dark (disaccommodation, DA) as well as when irradiated (photomagnetic effect, PE) with white light. All materials investigated exhibit DA and PE at 77 K, whereas in some cases effects occur at room temperature. The origin is attributed to domain wall pinning by magnetically anisotropic Co²⁺ ions that exchange electrons with Co³⁺ or other (V⁵⁺, Mn³⁺) ions. In view of the wide separation between the cobalt ions (?30 Å) the charge transport via iron ions is supposed to play an essential part.For a sample with higher cobalt dope the shape of the hysteresis loop at 77 K changes in the dark and the change can be hastened by irradiation. This phenomenon is attributed to the growth of a uniaxial anisotropy in the bulk of the material by Co²⁺, Co³⁺ ordering.From the electric resistivity of certain V and Si doped YIG materials it is concluded that V⁵⁺ ions oxidize Fe²⁺ ions according to V⁵⁺+Fe²⁺ → V⁴⁺+Fe³⁺.     

ESR and photoacoustic spectra of V2O5−MO2 (M = Se, Te, Ge) glasses

ESR spectra of V₂O₅?MO₂ (M = Ge, Se, Te) glasses are investigated in the range 298–498 K. The spectra at 298 K are characteristic of V⁴⁺ with the 3d¹ electron localized on a single ${}^{51}\text{V}\text{(I =}\text{7}\text{2}$) in the glass network. At higher temperature, the hyperfine structure progressively broadens, leading eventually to a broad, single ESR peak. These results are consistent with thermally-induced electron hopping from V⁴⁺ to V⁵⁺. Photoacoustic spectra of the glass at 298 K are characteristic of V⁴⁺ in a distorted octa environment. A correlation of ESR and PAS data suggests that covalency increased as M is charged from Ge through Te to Se.     

The fabrication and characterization of 4H SiC power UMOSFETs

The fabrication of 4H-SiC vertical trench-gate metal-oxide-semiconductor field-effect transistors(UMOSFETs) is reported in this paper.The device has a 15-μm thick drift layer with 3×1015 cm-3 N-type doping concentration and a 3.1μm channel length.The measured on-state source-drain current density is 65.4 A/cm2 at Vg = 40 V and VDS = 15 V.The measured threshold voltage(Vth) is 5.5 V by linear extrapolation from the transfer characteristics.A specific on-resistance(Rsp-on) is 181 mΩ·cm2 at Vg = 40 V and a blocking voltage(BV) is 880 V(IDS = 100 μA@880V) at Vg = 0 V.     

Monitoring by Mössbauer spectroscopy the thermal reduction of hematite into magnetite: the surface effect and charge disproportionality in iron oxide nanoparticles

Nanoparticles of magnetite Fe₃O₄ were synthesized by thermal reduction of hematite α-Fe₂O₃ powder in the presence of high boiling point solvent. The structural transformations and magnetic properties of the obtained nanoparticles were investigated by the ⁵⁷Fe Mössbauer spectroscopy, X-ray diffraction, and magnetic measurements. The content of hematite and magnetite phases was evaluated at each step of the chemical and thermal treatment of the product. An increase of saturation magnetization with the reaction time correlates with an increase of concentration of magnetite in the samples. The electron hoping between Fe^2?+? and Fe^3?+? ions in the octahedral sites of the magnetite nanoparticles and Verwey phase transition were investigated. It was established that not all iron ions in the octahedral sites participated in electron hoping Fe^2?+????Fe^3?+? above the Verwey temperature T _V, and the charge distribution could be expressed as $\big( {{\rm Fe}^{3+}}\big)_{{\rm tet}} \big[ {{\rm Fe}_{1.85}^{2.5+} {\rm Fe}_{0.15}^{3+} }\big]_{{\rm oct}} {\rm O}_4$ .     

Electric quadrupole nuclear orientation of182Ta as graphite intercalation compound TaCl5

Nuclear orientation of¹⁸²Ta achieved by electric quadrupole interaction in TaCl₅ molecules intercalated in oriented graphite crystals has been observed. Assuming the electric field gradient V_zz along the c-axis and proper intercalation yields V_zz=+0.32 (4)×10¹⁸V/cm². Other possibilities and sources of reduction of the nuclear orientation effect are considered.     

129Te Mössbauer emission spectroscopic study of the V-Te system: V3Te4, V5Te8 and VTe2 phases

The hyperfine interaction in the VTe system (V₃Te₄, V₅Te₈ and VTe₂ phases) was studied by means of the ¹²⁹Te Mössbauer emission spectroscopy. The transferred magnetic hyperfine field at the ¹²⁹I site was observed at 16K for the V₅S₈-type V_2.60Te₄ which has T_N at 52K. It was found that the ionicity estimated from the isomer shift decreases with decreasing the vanadium content, which is in better agreement with the earlier results on similar chalcogenide systems such as CrTe.     

Microscopic magnetic properties of (V1−xTix)2O3 near the phase boundary of the metal–insulator transition

Magnetic susceptibility (χ) and ⁵¹V NMR have been measured in (V_1−xTi_x)₂O₃ near the phase boundary of the metal–insulator transition. It is established that the transition from antiferromagnetic insulating (AFI) to antiferromagnetic metallic phases near x_c≈0.05 is not quantum critical, but is discontinuous with a jump of the transition temperature. In the AFI phase at 4.2 K, we observed the satellite in the zero-field ⁵¹V NMR spectrum around 181 MHz in addition to the ‘host’ resonance around 203 MHz. The satellite is also observable in the paramagnetic metallic phase of the x=0.055 sample. We associated the satellite with the V sites near Ti, which are in the V³⁺-like oxidation state, but has different temperature dependence of the NMR shift from that of the host V site. The host d-spin susceptibility for x=0.055 decreases below ∼60 K, but remains finite in the low-temperature limit.     

小尺寸VmOn+团簇的激光光解和密度泛函计算

通过激光溅射法产生了V₂O_n⁺ (n=1, 2), V₃O_n⁺ (n=1, 2, 3)和V₄O₃⁺等缺氧的钒氧团簇,并采用532和266 nm波长的激光对它们进行了光解研究. 利用密度泛函理论计算与激光光解实验相结合确定了这些团簇的几何结构和可能的光解通道. 激光光解实验表明V相似文献