Precision measurement of the electric quadrupole interaction in zinc metal

To decide on the validity of various values for the quadrupole coupling constant of Zn metal available in the literature, we have used the frequency modulation technique to the 93.3 keV Mössbauer resonance of⁶⁷Zn. We obtained for a⁶⁷Zn metal absorber: e²qQ/h =v _O = 12.34 ± 0.03 MHz. The asymmetry parameter was found to be =0.00 _–0 ^+0.06 . These precise values can be used as a calibration standard for⁶⁷Zn Doppler drives.This work has been supported by the Bundesministerium für Forschung und Technologie and by the Kernforschungszentrum Karlsruhe.     

Nuclear quadrupole interaction of199mHg-ferrocenethiol complexes

We determined the^199mHg nuclear quadrupole interaction (NQI) by time differential perturbed angular correlation in the following ferrocenethiol complexes with mercury: ferrocenethiol (v _Q =1253(4) MHz, =0); 1,1-ferrocenedithiol (47%v _Q =1555(8) MHz, =0.13(2); 25%v _Q =726(19) MHz, =0.81(2); rest unspecific); 2-ferrocenyl-ethanethiol (v _Q =1306(6) MHz, =0.17(1)); and a 1, 1-bis (2-mercapto-propylthio)ferrocene oligomer (v _Q =1411(5), =0). All NQIs are rather large with small asymmetry parameters, indicating essentially linear S-Hg-S bonds. The only exception is the minority fraction in 1,2-ferrocenedithiol which suggests the formation of a 1,3-dithia-2-mercura[3]ferrocenophane.     

The martensitic phase transition in NiTi

The technique of perturbed angular correlation of gamma rays (PAC) was applied to study the martensitic phase transition of a shape-memory-effect alloy Ni_49.9Ti_50.1 doped with¹¹¹In/Cd probe atoms. Spectra measured above and below the martensite starting temperature,M _s 340 K, exhibit quadrupole interactions of probes at cubic and noncubic lattice sites, consistent with the respective crystal structures. Unlike spectra measured belowM _s those measured above exhibit a large frequency distribution attributed to lattice displacement waves observed in diffraction studies. Analysis tentatively suggests that the waves are dynamic and not static. BelowM _s, at 290 K, a static quadrupole interaction was observed with coupling frequency ₁=34 Mrad/s and asymmetry parameter =0.18, increasing to ₁=40.5 Mrad/s and =0.34 at 77 K.     

The electric field gradient and its temperature dependence at111Cd in α-Uranium

The magnitude and temperature dependence of the quadrupole interaction at the¹¹¹Cd site in orthorhombic -Uranium was investigated between 293 and 17 K. The parent activity¹¹¹In was implanted into Uranium metal with an energy of 80 keV and the - TDPAC technique, applied to the 245 keV state in¹¹¹Cd, was used to measure the quadrupole interaction frequency. The derived electric field gradient for Cd in Uranium was found to be highly asymmetric (=1) and led to a quadrupole interaction frequency of _Q=7.10(7) MHz at 293 K. The temperature dependence of the quadrupole interaction is very strong, _Q increases to 14.3(2) MHz at 17 K and shows a linear dependence on the temperature.This work has been partially supported by the BMFT, FRG (03B01B0N/2).Work performed under the auspices of the U.S. Department of Energy by the Lawrence Livermore National Laboratory under contract number W-7405-ENG-48.     

Intrinsic point defects in niobium: Trapping at100Pd and111In impurities observed by PAC

Radiation-induced lattice defects in high-purity niobium have been investigated in the temperature range of 30K to 540 K by means of - perturbed angular correlation (PAC) measurements using the radioactive probes¹⁰⁰Pd/¹⁰⁰Rh and¹¹¹In/¹¹¹Cd. Both probes were produced within the niobium samples by means of heavy-ion nuclear reactions. At the Pd impurities trapping of defects occurred during heavy-ion irradiation at about 30 K in two defined configurations: defect 1(Pd) withv _Q1=e ² qQ/h=42(±2) MHz, ₁=0 and defect 2 (Pd) withv _Q2=(±2) MHz, ₂=1. Two defects were observed at the In impurities in annealing stage III (around 250 K) after heavy-ion as well as electron irradiations: defect 1(In) withv _Q1=87(±1) MHz, ₁=0 and defect 2(In) withv _Q2=105(±2) MHz, ₂=0.65(±0.02). A third defect (defect 3(In):v _Q3=177(±2) MHz, ₃0.2) appeared above 260 K after heavy-ion irradiation only. The data are interpreted in terms of interstitial trapping at the Pd impurities and vacancy trapping at the In impurities. Information on the microscopic structure of defect 1(In) and 2(In) is obtained from a PAC-single-crystal experiment. For defect 1(In) axial 111-symmetry is found, which leads us to identify this defect with a monovacancy as nearest neighbor with respect to the In probe. Defect 2(In) is the trapped divacancy for which an orientation is found that is consistent with both vacancies being nearest neighbor to the probe but second nearest neighbors to each other.     

Molecular field effects in Mössbauer spectra of FeSb2O4

Mössbauer effect measurements have been made using⁵⁷Fe in FeSb₂O₄. At liquid helium temperature a combined electric quadrupole and magnetic hyperfine interaction is observed withH _eff=185±2 kOe, 1/2e ² qQ=2.94±0.09 mm/sec and =0.37±0.09. The direction ofH _eff is perpendicular to thec axis of the crystal and at 33° to the <110> direction. Thec axis is determined to be the direction of the intermediate principal EFG tensor axis. Calculations are made using a molecular field term in the Hamiltonian for the Fe²⁺ orbitals. The results of these calculations are used to explain the observed values of 1/2e ² qQ and and permit a determination of the ordring of the T_2g orbitals among the T_2g energy levels.     

Quadrupole interaction at57Fe in zirconium metal

The nuclear quadrupole interaction at⁵⁷Fe nuclei in hcp -zirconium metal is measured in the temperature range 4.2 to 560 K using Mössbauer spectroscopy of⁵⁷Fe. The quadrupole splitting at room temperature is measured to be 0.660(8) mm/sec which corresponds to an electric field gradient of |eq|=3.17×10¹⁷ V/cm² at the⁵⁷Fe nucleus in a -Zr host. As has been observed in many other systems, the results show significant electronic contributions. The temperature variation of the quadrupole interaction is much stronger than is expected from the lattice contributions and is found to follow theT ^3/2 dependence approximately.⁵⁷FeZr does not follow the universal correlation betweeneq _ion andeq _el observed in most of the normal metal hosts but follows the trends recently observed by Krusch and Forker for the transition metal hosts. Our results are compared with the predictions of the conduction electron charge shift model recently proposed by Bodenstedt and Perscheid.     

PAC investigation of77Br→77Se on silicon surfaces

The perturbed-angular correlation (PAC) method has been applied to investigate the sites occupied by isolated⁷⁷Br-atoms on silicon surfaces. The nuclear quadrupole interaction was used to determine the electric field gradients (efg) acting at the 5/2^– state in⁷⁷Se, populated in the⁷⁷Br decay. For the Si(100)2×1 surface two different field gradients have been observed with the parameters _Q1 = 583(5) MHz, ₁ = 0.0(1) and _Q2=543(5) MHz, ₂ = 0.40(3). Typical values for the Si(111)7×7 surface from preliminary data are _Q=548(9) MHz,=0.54(6). These electric field gradients are identified with adsorption sites of the selenium at dangling bonds of the silicon surfaces.     

TDPAC studies of internal AgIn alloy oxidation

The internal oxidation of dilute AgIn alloys in open air versus In concentration and oxidation temperature was investigated by the TDPAC technique. The¹¹¹In interaction described by the broad quadrupole frequencies distribution aroundv _Q = 115 MHz and =0.5–0.7 was observed and interpreted as due to nonstoichiometric In–O_X cluster formation. For higher temperatures and more concentrated alloys additionally quasiunique frequencyv _Q 157 MHz with 0.28 was evidenced and ascribed to¹¹¹In interaction inside In₂O₃ precipitates. The internal oxidation under reduced oxygen pressures was studied and the thermal stability of the complex formed was tested. The effect of surface preparation on internal oxidation was observed.     

Indium metal nanoclusters studied by PAC

The technique of perturbed angular correlations of gamma rays (PAC) is applied for the first time to study the structure of small metal clusters. Metal clusters containing¹¹¹In probe atoms with 50 nm radii were synthesized by dissolving InCl₃ containing¹¹¹In in hexane using a surfactant, thereby creating an inverse micellar solution. The salt was then reduced to metal form by addition of NaBH₄. 100% conversion efficiency of In salt to metal clusters was achieved. PAC measurements at 293 K on the¹¹¹Cd daughter nuclide exhibited a nuclear quadrupole interaction with coupling frequency ₀=16.0(5) Mrad/s and a small asymmetry parameter, =0.20(4). The frequency is as observed for bulk In crystals, but a non-zero value of has not been previously reported. Lack of inhomogeneous signal broadening and the faceted shape of some nanoclusters suggest high crystal perfection.     

Nuclear orientation study of the quadrupole interaction for Co in PdCo alloy

The angular distribution anisotropy of -radiation was measured following the decays of⁵⁸Co and⁶⁰Co oriented at low temperatures in the ferromagnetic PdCo alloy. The ratio of the electric quadrupole to magnetic dipole interaction constants for the⁶⁰Co was deduced to be P/a_o=0.001±0.003, where P=3e²qQ/4I(2I-1) and a_o=H/I.     

On the directional dependence of composite field operators

The Wilson expansion of the field operator productA ₁(x ₁)A ₂(x ₂) may be used to define composite operators which are local with respect to 1/2(x ₁+x ₂) and depend in addition on a vector proportional to the distancex ₁–x ₂. It is proved that the composite operators are polynomials in , for fixed ² 0, and that their dependence on ² only involves powers of ² and lg².This work was supported in part by the National Science Foundation Grant No. GP-25609.     

Mass and Γ3π0/Γγγ decay branching ratio of theη-meson from the p(γ, η)p reaction

Near threshold photoproduction of-mesons from the proton has been measured at the MAMI accelerator with the TAPS spectrometer. The mass of the-meson was deduced from the threshold energy for-photoproduction. The result of m =(547.12 ± 0.06 ± 0.25) MeV supports the low value of the-mass reported from a dp ³He measurement at SATURNE in 1992. The-decay branching ratio ₃0/ was measured to be (0.832±0.005±0.012).This article was processed by the author using the L^AT_EX style filepljour2 from Springer-Verlag.     

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.     

Hyperfine Interactions at 181Ta in Hf2Co7

In this paper we report a time differential perturbed angular correlation (TDPAC) study of hyperfine interactions at ¹⁸¹Ta in Hf₂Co₇ compound. The TDPAC measurements have been performed in the temperature range 77–1023K. The measured spectra showed broad distribution of hyperfine interactions up to 388K. Above this temperature, in a reversible manner, two nuclear electric quadrupole interactions (EQI) have been observed: at 393K, _Q1=449.0(27)MHz, ₁=0.00(4) and _Q2=144.7(41)MHz, ₂=0.44(2). Since the Curie temperature for this compound is known from the literature to be around 420K, only magnetic order transition could be responsible for such an observation. However, the measurements of magnetization did not exhibit any drastic change in this temperature range.     

Distribution of nuclear quadrupole splittings in amorphous materials and the topology of the (Vzz, η)-parameter space

In structural investigations of amorphous materials by determination of nuclear quadrupole splittings, the connectivity of the region of non-zero probability density in the space of the splitting parameters V_zz and is important. The conventional presentation of the parameter plane conceals the continuous connection between regions of positive and negative V_zz via the common boundary defined by =1. A new conceptual view of the (V_zz, )-plane is proposed which clearly expresses its topological structure.     

The electric field gradient at iodine impurities in zinc and cadmium

The electric quadrupole interaction at iodine implanted in zinc and cadmium single crystals is investigated, using the - perturbed angular correlation technique. The results show that the implanted¹²⁹Te and¹³²Te isotopes occupy two well-defined sites, identified by the electric field gradient parameters. One fraction of the impurities is substitutionally implanted, witheq _zz=–1.49(9)10¹⁸ and –1.58(15)10¹⁸V/cm², in Zn and Cd respectively. The other fraction is identified as an impurity-divacancy configuration with |eq _zz |=3.81(8)10¹⁸V/cm²; =0.72(4) for Zn and |eq _zz |=3.55(11)10¹⁸V/cm²; =0.53(13) for Cd. The electronic enhancement in the electric fieldgradient at the substitutional site equalsK=–0.66 and –0.56 respectively and follows the empirical trend ofK versus the impurity valence for the s-p elements in Zinc.     

39K NMR study of the low temperature phase transitions in KLiSO4

The³⁹K NMR spectra, spin-spin (T ₂) and spin-lattice (T ₁) relaxation times of KLiSO₄ have been measured in the temperature range from 300 K to 90 K. The temperature dependence of the³⁹K (I=3/2) NMR spectra demonstrates the occurrence of a first order phase transition atT _c1=217 K which occurs without a change in the K⁺ site symmetry and another first order transition atT _c2=190 K which is connected with a lowering of the K⁺ site symmetry and the formation of three kinds of ferroelastic domains. From the angular dependence of the second order quadrupole shifts of the³⁹K NMR 1/2–1/2 transitions the electric-field gradient (EFG) tensors at the potassium sites were determined at 290 K, 204 K and 180 K. The symmetry of the ferroelastic phase is monoclinic and not orthorhombic as the K⁺ EFG tensors are tilted away from thec-axis belowT _c2. TheT ₁ data further show the freezing in of the slow reorientational motion 10^–8 s with decreasing temperature from 300 to 90 K.On leave from: J. Stefan Institute, E. Kardelj University of Ljubljana, Ljubljana, Yugoslavia     

39K quadrupole coupling and spin-lattice relaxation in the high temperature phases in KLiSO4

³⁹K quadrupole perturbed nuclear magnetic resonance spectra show that in KLiSO₄ atT _c =743 K a phase transition from a room temperature hexagonal to a high temperature orthorhombic phase takes place. The high temperature phase is definitely not incommensurately modulated. The huge shortening of the³⁹K spin-lattice relaxation time on approachingT _c from below demonstrates that KLiSO₄ becomes a superionic conductor above 743 K. The self-diffusion coefficient of the Li-ions is estimated asD=10^–6 cm²/s at 780 K.     

Mössbauer effect of iodine at pressures to 30 GPa

We report the first high pressure¹²⁹I Mössbauer measurements with elemental iodine at pressures to 30 GPa. A 20 mg/cm^{2 129}I₂ absorber was mounted in a diamond anvil cell with an effective diameter of 0.21 mm. The source used was Mg₃ ^129mTeO₆. Experiments were performed mainly at 4 K and the pressure was monitored by the ruby fluorescence method. With increasing pressure we observe a gradual decrease in ¦e²qQ¦ and an increase in IS and values of the low pressure, molecular phase; at 16 GPa a new phase (HP1) is detected characterized by a change in sign of e²qQ and a smaller value of ¦e²qQ¦, and a substantial increase in . At 24 GPa a new phase (HP2) is formed that is characterized by a smaller value of . In general the population of the molecular phase decreases from 1.0 near 15 GPa to a value of 0.4 at 30 GPa. The fraction of the high pressure phase (HP1 + HP2) increases at the expense of the molecular phase and that of the HP2 at the expense of the HP1 phase. These observations are discussed in relation to the onset of a metallic phase near 16 GPa and recent x-ray diffraction studies.Work performed under the auspices of the U.S. Department of Energy.