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 Mg and Zn detected by β-emitters,8Li and12x0392;x0392;x0392;

The quadrupole coupling constants of⁸Li and¹²B in hcp Mg and Zn are determined by use of a newly developed nuclear quadrupole resonance technique (NNQR) as ¦eqQ(⁸Li in Mg)/h¦=3.0±0.3 kHz, ¦eqQ(⁸Li in Zn)/h¦=33.5±2 kHz, and ¦eqQ(¹²B in Mg)/h¦=47.0±0.1 kHz. Correspondingly, the electric field gradients at room temperature are deduced: ¦q(⁸Li in Mg)¦=(3.81±0.39)×10¹⁸, ¦q(⁸Li in Zn)¦=(4.25±0.27)×10¹⁹, and ¦q(¹²B in Mg)¦=(1.47±0.03)×10²⁰, all in V/m². The experiments are compared with the results of first-principles super-cell band structure calculations which can treat local lattice relaxations around the impurity nuclei. The calculations show that the most favorable location of these light interstitials in hcp Mg is not the octahedral-like sites which have the biggest interstitial volume, but the basal trigonal sites with a local lattice expansion of as big as 30%. Calculated electric field gradients at the impurity nuclei reproduce the experimental values fairly well.     

NMR spin echoes and quadrupole effects in nickel single crystals

NMR spin echo measurements of naturally abundant⁶¹Ni have been performed with Néel-type nickel single crystals at 4.2 K. The NMR excitation condition could properly be chosen in order to get signals either from nuclei situated within magnetic domains or within domain walls. In both cases a quadrupole splitting of the NMR line could be observed. By applying an external magnetic field, the direction of the domain magnetization could be varied with respect to the fcc crystal lattice. From the variation of the quadrupole splitting with the crystallographic direction, the tensor of the electric field gradient (EFG) has been derived. The quadrupole splittings and the corresponding field gradients in the principal axis system of the EFG are: Δv_Q kHz, Δv_Q kHz, Δv_Q kHz, V_<111>=(6.6±0.5)·10¹⁸ V/m², V_<110>=4.6±0.5)·10¹⁸ V/m², V_<112>=(2.0±0.5)·10¹⁸ V/m².     

Transferred hyperfine field in the pseudo-binary compound Y(Fe,Mn)2

The NMR of⁸⁹Y in Y(Fe_1−xMn_x)₂ has been observed. Two kinds of Mn moments were estimated by analyzing the⁸⁹Y hyperfine field: (1) the low spin state with about 0.6 μ_B in antiparallel to Fe moment and (2) the high spin state with about 2.8 μ_B in parallel to Fe moment. The magnetizations estimated from NMR results are in good agreement with those of magnetization measurements.     

Residence sites of fluorine in crystalline silicon and highly oriented pyrolytic graphite

Measurements of the electric field gradient (efg) at F impurity sites in crystalline silicon and highly oriented pyrolytic graphite (HOPG) have been compared with cluster model calculations using both Hartree-Fock (HF) and density functional theory (DFT) formalisms. The technique of time-differential perturbed angular distributions of -ravs was employed to derive the efg parameters following implantation of¹⁹F via the¹⁹F(p, p)¹⁹F^* reaction. For the case of HOPG the DFT method gave closer agreement with the experimental values of ¦V _zz¦=3.24(14)×10²²V/m² and=0.16(3), yieldingV _zz=–3.09×10²²V/m²and=0.13 for¹⁹F at a site between the layers with point group symmetry C_2h and inter-layer spacingd=3.70 Å. For¹⁹F implantation in silicon three sites were found corresponding to quadrupole frequencies 23.2(3) MHz, 35.2(3) MHz and 37.1(5) MHz. Both HF and DFT calculations are consistent with the assignment of interstitial antibonding and bond centre sites for the 23.2 and 35.2 MHz, respectively. In the former case, the F atom is located 1.81 Å along a <111> direction from a silicon atom; in the latter situation the Si-Si bond length is found to expand by 1.02 Å from its normal lattice value. It is speculated that the third interaction, which occurs at only the 10% level, possibly arises from sites associated with a defect or other impurity. To achieve a reduction in cluster size, the completion of dangling bonds with atoms other than hydrogen was investigated. The results were found to be comparable.     

2H-NMR study of ammonium ion rotational tunneling and reorientation in (ND4)2SnCl6 single crystal: I. Tunneling frequency measurements

Theory of²H-NMR spectra is developed for a ND ₄ ⁺ ion. Quadrupole and dipole-dipole interactions for four deuterons of the tetrahedral ion as well as the rotational tunneling are taken into account. Features in the single crystal spectra at the high magnetic field of 6.7 T are analyzed. Their central doublets (±5 kHz range around the Larmor frequency) are attributed to theA symmetry species and exhibit sensitivity to theA–T tunneling frequencyv _t . This allows the measurement ofv _t in a wide rangev _t <10 MHz. The shape of sidebands (±140 kHz range) is related to the T levels structure. Theoretical predictions are verified on a (ND₄)₂SnCl₆ single crystal at 44 MHz. The tunneling frequency at temperatures below 10 K equals 7.5 MHz, which is about 100 times smaller than for (NH₄)₂SnCl₆.v _t was measured up to 40 K. At still higher temperatures motional narrowing effects were observed for theA spectral components preventing the determination ofv _t .     

Mössbauer spectroscopy of a semiconductive phosphate glass (10V2O5 30Fe2O3 60P2O5 at low temperature

In order to clarify the difference between the local structures of Fe³⁺ and those of Fe²⁺ ions in a semiconductive phosphate (10V₂O₅-30Fe₂O₃-60P₂O₅) glass, the temperature dependencies of the isomer shift (IS), quadrupole splitting (QS) and absorption area (AR) for Fe³⁺ and Fe²⁺ ions were measured. Debye temperatures ( _D) for Fe³⁺ and Fe²⁺ ions were determined to be 318 ± 29 K and 223 ± 18 K, respectively, from the temperature dependence of the absorption area (AR). From the temperature dependence of the quadrupole splitting(QS), B strength parameters for Fe³⁺ and Fe²⁺ ions, which are the coefficients for theT ^3/2 term, were deduced. It was found that in this phosphate glass, Debye temperatures _D(AR) were consistent with those obtained using the relation of the B parameter to Debye temperature described in the literature. Also from the temperature dependence of the isomer shift, the difference between the thermal effects except the second-order Doppler shift for Fe³⁺ ions and those for Fe²⁺ ions was compared.     

Quadratic crystal field tensors and spin Hamiltonian tensors of Fe3+ in Li2Ge7O15 above and below the phase transition temperature

Dopant Fe³⁺ ions in tetrahedral and octahedral positions of Ge⁴⁺ in the crystal Li₂Ge₇O₁₅ were studied using EPR. Fe³⁺ substitutes for Ge⁴⁺ with a local charge compensation. The octahedral site and the tetrahedral sites significantly differ by the value of the invariant sumS(B ₄) of theB ₄ tensor of the spin Hamiltonian of Fe³⁺. The irreducible tensor products {V ₄ ? V ₄}₄ and {V ₄?V ₄}₂ theV ₄ tensor of the crystal field calculated using the point-charge model for octahedral and tetrahedral complexes provide the predominant contribution of the crystal field to theB ₄ andB ₂ tensors of the spin Hamiltonian of Fe³⁺, respectively. A comparison of the fourth-rank tensorsB ₄ of the spin Hamiltonian and {V ₄?V ₄}₄ of the crystal field determined at 300 K with those determined at 77 K supports the conclusion that the phase transition is accompanied by combined rotation of the [GeO₄] tetrahedra with the [Ge(1)O₆] octahedron almost unaltered. The spectrum lines are narrow and the variety of point defects in the vicinity of the paramagnetic impurity ions Fe³⁺, Cr³⁺ and Cu²⁺ is not detected. These facts are inconsistent with the statistically distributed model for the Li(2) atom. In specific cases at 300 K, when the wings of the two spectrum lines of theM→M+1 and theM+2 →M+3 transitions of Fe³⁺ ions belonging to one system of translationally equivalent positions overlap an extra line appears in the center between these lines. It is suggested that this effect is due to the soft phonon mode above the phase transition temperature.     

Mössbauer spectroscopy on RE2Fe14BHx (RE-Y,Ce, Dy,Er) alloys

RE₂Fe₁₄B alloys and some of their hydrides have been studied through⁵⁷Fe and¹⁶¹Dy Mössbauer spectroscopy (MS). For both the paramagnetic and ordered phases a consistent and physically sound analysis of the⁵⁷Fe spectra is presented. Fe hyperfine fields and the local magnetic moments are obtained and compared with magnetic and structural data. A spin reorientation is observed for Er₂Fe₁₄B. A constant collinear structure down to 4.2 K was determined for the other samples. The¹⁶¹Dy spectra are interpreted for a pure ¦J_Z=15/2 > ground multiplet in Dy₂Fe₁₄B and its hydride. The B₂ crystal field parameters were estimated empirically for the Dy-alloy. Their values can account for the anisotropy in the compounds.     

X-Band ESR and51V NMR study of the Haldane system PbNi2−xMgxV2O8

The temperature and angular dependence of the X-band electron spin resonance (ESR) and⁵¹V nuclear magnetic resonance (NMR) spectra have been measured in a recently discovered Haldenegap system, PbNi_2-xMg_xV₂O₈ (0≤x≤0.24). The angular dependence of the ESR signal suggests that both the spin diffusion as well as the magnetic anisotropy determine the electronic spin correlation functions. However, in doped samples the magnetic anisotropy increasingly dominates the spin dynamics on cooling. The huge broadening of the⁵¹V NMR spectra in doped samples at low temperatures provides evidence for localized magnetic moments in the vicinity of the Mg impurities. Locally distorted structure around each Mg impurity may slightly modify the magnetic interactions and be potentially responsible for the antiferromagnetic ordering (belowT _N≈ 3.5K) in doped compositions.     

The hyperfine interaction of gadolinium and holmium in cubic Ho: (Gd,Ce)Fe2 compounds

The low-temperature hyperfine parameters of the ferrimagnetic C15 intermetallic system Ho_0.03Ce_xGd_0.97-xFe₂ have been measured at Gd using the 87 keV γ-ray of ¹⁵⁵Gd and at Ho using spin echo nmr of ¹⁶⁵Ho. A linear decrease of the hyperfine field B_t with increasing x is observed, the slope being almost the same for both nuclei. The observed slope (dB_t/dx ? -37T) is nearly three times greater than that found for ¹⁵⁵Gd in the analogous H₀:(Y, Gd)Fe₂ system; this is attributed to the influence of the increased conduction electron density when trivalent lanthanide ions are replaced by Ce⁴⁺.     

Mössbauer and molecular orbital (MO) study of localized and delocalized mixed-valence organo-FeIIFeI bisandwiches

A Mössbauer study of two mixed-valence Fe^IIFe^I compounds C₅H₅Fe(C₅H₄)₂ FeC₆(CH₃)₆ (1) and ¦C₆(CH₃)₆ Fe(C₅H₄)₂ Fe C₆(CH₃)₆¦⁺ (2 ⁺) was carried out from 4.2K to room temperature. Zero-field spectra show two types of iron atoms for1 and one type for2 ⁺. Hence1 is a localized mixed-valence complex and2 ⁺ a delocalized mixed-valence complexe. High magnetic field spectra for 2⁺ give a negative sign for the EFG and show the valence electron is delocalized on the two centers. IEHT-MO calculations confirm the results and allow to explain the temperature independence of the quadrupole splitting (QS) of2 ⁺.     

Mössbauer study of the ternary system (Fe1−xVx)3 Ge

Three crystallographically different structures of (Fe_1–xV_x)₃ Ge have been studied by⁵⁷Fe Mössbauer spectroscopy. The hexagonal phase, stable for low values ofx, is ferromagnetic with the spins parallel to thec-axis above a critical temperature, where a spin flip to thec-plane takes place. A V/Fe substitution in the near surrounding of an iron atom leads to a decrease in the isomer shift of –0.02 mm/s and an estimated reduction in the magnetic moment of 0.31 _B from 2.07 _B. A result for the intermediate cubic closed packed structure is that V populates only one type of metal sites. Furthermore, from similarities with-Fe the average value of the change in isomer shift is found to be +0.075 mm/s and +0.02 mm/s per Ge/Fe substitution in the 1nn and 2nn shells, respectively. The spin polarization effect on the magnetic hyperfine field for iron is –8.6%, –0.4%, and –0.6% per Ge/Fe (1nn), Ge/Fe (2nn) and V/Fe (3nn) substitutions, respectively. The simple cubic compound (Fe_0.7V_0.3)₃ Ge is non-magnetic down to at least 5 K. Here a decrease in the isomer shift of –0.05 mm/s is found for a V/Fe (1nn) substitution.On leave from the Department of Nuclear Physics, University of Madras, Madras, India.On leave from the Physics Department, Punjabi University, Patiala, India.     

Measurements of theP 3/2-S 1/2-intervals in then=4,n=5 andn=6 states of ionized helium

TheP _3/2-S _1/2-intervals in then=4,n=5 andn=6 states of ionized helium have been measured by a radio frequency method, which permits to determine the disturbing electric fields in the interaction region and to correct their influences. The experimental results for theP _3/2-S _1/2 intervals in then=4,n=5 andn=6 states were (20,180.6±0.8) MHz, (10,332.9±1.4) MHz and (5,979.1±1.2) MHz respectively. From these intervals, the following indirect values for theS _1/2-P _1/2-Lambshifts can be deduced: (1,768.5±0.8) MHz in then=4 state, (905.0±1.4) MHz in then=5 state and (524.3±1.2) MHz in then=6 state. The results agree with the theoretical predictions. The static electric fields in the interaction region, ranging from 2 to 6 V/cm, increased with increasing electron excitation current, but were independent of the helium pressure within the range of 10 to 26 mTorr. All uncertainties are expressed as 68% confidence values.     

Mössbauer and magnetic studies of BaVS3 and V5S8 doped with 57Fe

Iron can be easily introduced in BaVS₃ and V₅S₈. It is located at the vanadium sites and has been used as a probe to analyse by Mössbauer effect the magnetic properties of its surrounding matrix. The electronic state of iron in this matrix has also been studied. It was found that in BaVS₃, the iron is in a low spin Fe³⁺ configuration $\text{(S =}\text{1}\text{2}\text{)}$. In V₅S₈ at 4.2 K, the iron is in low spin Fe²⁺ configuration (S = 0). The rapid decrease of quadrupole splitting observed between 50 and 200 K is attributed to a thermally activated change in electronic structure. The high temperature configuration (above 200 K) seems to be neither pure low spin Fe³⁺ nor high spin Fe²⁺, but a mixture of configurations fluctuating at a rate which is faster than the characteristic time of Mössbauer measurements.     

Study of [Fe(pyim)3] complexes: dynamic spin equilibrium on encapsulation in zeolite Y

Tris complex of Fe^II2(2′-pyridyl)imidazole has been encapsulated in the supercages of zeolite Y and characterized by using powder XRD, FTIR, Mössbauer spectroscopy, variable temperature magnetization and MAS NMR techniques and results have been compared with those obtained for this complex with ClO₄⁻ and SO₄²⁻ as anions. At room temperature, the [Fe(pyim)₃](ClO₄)₂ complex exhibited low spin state, while [Fe^II(pyim)₃]SO₄ exhibited the existence of both low and high spin states. The encapsulated [Fe^II(pyim)₃]²⁺ complex exhibited a broad quadrupole doublet characterized by isomer shift, δ=+0.55 mm/s and quadrupole splitting ΔE_q=1.26 mm/s. The magnetization measurements carried out for the encapsulated [Fe^II(pyim)₃]²⁺ complex showed a systematic decrease in its values with decreasing temperature down to 75 K with no indication of thermal hysteresis effects. These results suggest the existence of a dynamic spin state equilibrium between the high and low spin states for the encapsulated [Fe^II(pyim)₃]²⁺ complex with time constant comparable to the characteristic Mössbauer time scale of ⁵⁷Fe nuclei.     

The mapon technique and recent developments

Typical linewidths observed in NMRON on dilute impurities in ferromagnetic metals are of order 1 MHz, making difficult the observation of structure in the resonance with splitting Δv much less than this value. The technique of Modulated Adiabatic Passage on Oriented Nuclei (MAPON) was recently developed as a means of measuring the weak electric quadrupole splitting Δv_Q of the nuclear hyperfine interaction due to an electric field gradient V_zz. MAPON has successfully been applied to measure Δv_Q as low as 4 kHz, i.e. less than 0.5% of the inhomogeneously broadened NMRON CWFM resonance line. The isotopes⁵⁶Co,⁵⁷Co,⁵⁸Co and⁶⁰Co have been studied in iron single crystal hosts, yielding Δv_Q consistent with known and estimated quadrupole moments. In addition the results to date give striking confirmation of analyses based on the single impurity relaxation model. Following a brief summary of the theoretical development of MAPON a review of experimental data is given for the CoFe<100> system. The variation of Δv_Q with direction of magnetization, measured in⁵⁸CoFe and⁶⁰CoFe single crystal samples, is also described. Further MAPON measurements are described for a⁵⁶CoFe polycrystalline sample, for which the most probable value and width of the distribution of V_zz can be described simply in terms of the single crystal principal axis results. The application of the MAPON technique to the measurement of nuclear electric quadrupole moments in implanted and diffused samples is discussed.     

The first principle study of magnetic properties of Mn2WSn,Fe2YSn (Y=Ti,V), Co2YSn (Y=Ti,Zr, Hf,V, Mn) and Ni2YSn (Y=Ti,Zr, Hf,V, Mn) heusler alloys

The spin polarized electronic band structures, density of states (DOS) and magnetic properties of Mn₂WSn, Fe₂YSn (Y=Ti, V), Co₂YSn (Y=Ti, Zr, Hf, V, Mn) and Ni₂YSn (Y=Ti, Zr, Hf, V, Mn) huesler compounds are reported. The calculations are performed by using full-potential linearized augmented plane wave method (FP-LAPW) within density functional theory. The magnetic trend in these compounds is studied using values of magnetic moments, exchange interaction and calculated band gap. The results reveal that Mn₂WSn and Ni₂VSn show 100% spin polarization, Co₂YSn (Y=Ti, Zr, Hf, Mn), Fe₂YSn (Y=Ti, V), and Ni₂MnSn exhibit metallic nature and Ni₂YSn (Y=Ti, Zr, Hf) and Co₂VSn show semi-conducting behavior.     

Electron paramagnetic resonance (EPR) and photo-EPR studies of aggregate centers with two iron atoms in silicon

We have investigated iron by EPR (electron paramagnetic resonance) and photo-EPR in initially boron doped silicon samples in which the iron concentration exceeded the boron content. A new EPR spectrum, showing orthorhombic-I symmetry was observed and could be fitted by an effective spin Hamiltonian with the parameters S=3/2, g=2.07, and E/D=0.68. We identify this spectrum as a new modification of a Fe₂B center which has the same symmetry but different configuration of the constituent atoms.Furthermore, we were able to determine the donor level of the old Fe₂B center to E=E_V+0.57±0.02 eV above the valence band.We have also investigated the Fe₂ donor. According to our straightforward interpretation the energy levels of the transitions from Fe₂⁺ to Fe₂⁰ and from Fe₂⁰ to Fe₂⁺ were determined as E=E_V+0.61±0.02 eV and E=E_C-0.67±0.02 eV, respectively, suggesting a lattice relaxation on electron capture, which is unusual for transition metal centers in silicon. PACS 71.55.Cn; 76.30.Fc     

G v,CKM unitarity,neutron decay; WR?

Superallowed Fermi beta-decay is analyzed in the light of new experimental data, new methodology and new treatment of the radiative and charge-dependent corrections. The following values are recommended:G _v /(c) ³=(1.13769±0.00091)×10^–5 GeV^–2;G _v ^* /(c) ³ =(1.15128±0.00084) × 10^–5GeV^–2 whereG _v is purged of radiative corrections suitably for combining withG to gain: ¦V _ud ¦=0.97539±0.00080 which leads to:¦V _ud ¦ ² +¦V _us ¦ ² +¦V _ub ¦²=1.0000+0.0017 and whereG _V ^* is the operational constant, incorporating the inner radiative correction, suitable for use in ordinary nuclear physics. It is noted that present results on the beta-decay of the neutron, when confronted by the above values, are inconclusive as to possible conflict with the minimal standard model and that judgement as to, for example, the intervention of a right-handed sector, should be suspended. The valueG _A ^* =1.2657±0.0030 is also recommended.