The nuclear quadrupole interaction at 111Cd and 181Ta sites in anatase and rutile TiO2: A TDPAC study

The nuclear quadrupole interaction of the I=5/2 state of the nuclear probes ¹¹¹Cd and ¹⁸¹Ta in the anatase and rutile polymorphs of bulk TiO₂ was studied using the time differential perturbed angular correlation (TDPAC) method. The fast–slow coincidence setup is based on CAMAC electronics. For anatase, the asymmetry parameter of the electric field gradient was η=0.22(1) and a quadrupole interaction frequency of ω_Q=44.01(3) Mrad/s was obtained for ¹⁸¹Ta. For rutile, the respective values are η=0.56(1) and ω_Q=130.07(9) Mrad/s. The values for rutile match closely with the literature values. In case of the ¹¹¹Cd probe produced from the beta decay of ¹¹¹Ag, the quadrupole interaction frequency for anatase was negligibly small as indicated by an unperturbed angular correlation in anatase. On the other hand for rutile the quadrupole frequency is ω_Q=61.74(2) Mrad/s and the asymmetry parameter η=0.23(1) for the ¹¹¹Cd probe. The results are interpreted in terms of the surrounding atom positions in the lattice and the charge state of the probe nucleus.     

Effect of Mg2+ on the Magnetic Compensation of Lithium–Chromium Ferrite

PAC measurements on ¹¹¹In(¹¹¹Cd) implanted and thermally treated α-Fe have shown an indication for a cubic defect with the ¹¹¹Cd probe in the centre of it. The measured room temperature (R. T.) magnetic hyperfine fields are B _hf1 = −38.4(8) T for substitution and B _hf2 = +11.5(3) T for the cubic defect. Additionally, probes with pure quadrupole frequency distributions were observed, which are incorporated in surface contaminations.     

TDPAC investigations of the111Cd quadrupole interaction in ternary chalcopyrite semiconductors

The quadrupole interaction at room temperature of¹¹¹Cd in CdSiP₂, CdGeP₂, and CdSnP₂ is investigated by^111mCd-TDPAC. The results are compared with those of former¹¹¹In(¹¹¹Cd) measurements. We observed axially symmetric quadrupole interactions with identical quadrupole coupling constants provided that radiation damage was annealed. This proves that also In probes are positioned at Cd-sites (A-sites) in these ternary compounds.     

Nuclear orientation of111m Cd in Zn and Be and the quadrupole moment of the 245keV state

The 48.7 m^111m Cd activity was implanted in Zn and Be single crystals which were soldered to the cold finger of a dilution refrigerator and kept below 0.2 K during implantation. Subsequent nuclear orientation experiments allowed the determination of the quadrupole interaction frequencyv _Q of the 11/2^? isomeric state of¹¹¹Cd in Zn and Be as ?139 (15) MHz and +43(16) MHz respectively. With these results we derive the quadrupole moment of the 5/2⁺ 245 keV level of¹¹¹Cd including sign asQ = +0.83(13) b and the sign of the electric field gradient for Cd in Be. The half-life of^111m Cd was redetermined as 48.67 (6) m.     

Ferromagnetic Semiconductors Studied by Hyperfine Interaction of Nuclear Probes

The ferromagnetic spinels CdCr₂Se₄ and CuCr₂Se₄ were investigated by PAC (perturbed angular correlations) after implantation of the probes ¹¹¹In(¹¹¹Cd), ^111mCd, ¹¹¹Ag(¹¹¹Cd) and ⁷⁷Br(⁷⁷Se). The site occupation of different probes was determined by magnetic and electric hyperfine interactions. Theoretical calculations of hyperfine parameters by the WIEN97 code gave satisfactory efg (electric field gradients) but the magnetic hyperfine fields are inconsistent with the experiments. This revised version was published online in September 2006 with corrections to the Cover Date.     

Optical pumping of the metastable 53P0 level of ODD isotopes of cadmium

Metastable 5³P₀ atoms of ¹¹¹Cd and ¹¹³Cd are optically pumped in an atomic beam. Their magnetic resonances are observed with Landé factors g(³P₀, ¹¹¹ Cd) = (1.090±0.003) × 10^-3 and g(³P₀, ¹¹³Cd) = (1.143 ± 0.003) × 10^-3 which are 1.7 times larger than the g-factors of the 5¹S₀ ground state. This large difference arises from a slight mixing of the 5³P₀ level with the 5³P₁ and 5¹P₁ levels through the hyperfine interaction.     

Hyperfine interactions of111Cd impurities in Cr2O3

The electric and (antiferro-)magnetic hyperfine interaction of¹¹¹Cd in α-Cr₂O₃ after¹¹¹In implantation was studied via PAC. Two fractions with axially symmetric electric field gradients were observed having antishielding factors of V_zz/V_zz ^pc=79(12) and 106(16), respectively. From the line broadening of the Fourier components of the first fraction its supertransferred magnetic field was estimated as B_loc (20 K)≤0.41 T, about two orders of magnitude smaller than for substitutional¹¹¹Cd in NiO and CoO.     

NMR detected by Mössbauer-effect,applied to the system57CoFe

The ratio of the Larmor frequencies of¹¹¹Cd and²H has been measured in an aqueous solution of CdSO₄ with high accuracy.¹¹¹Cd chemical shifts have been investigated in aqueous solutions of CdCl₂, Cd(NO₃)₂, CdSO₄, and Cd(ClO₄)₂ as a function of concentration. Using these, the ratio of the Larmor frequencies of the¹¹¹Cd nuclei for infinite dilution relative to²H in pure D₂O is given. From this ag _I -factor for¹¹¹Cd has been derived and has been compared with theg _I -factor of an optical pumping experiment. The resulting shielding constant is σ^*(hydrated¹¹¹Cd versus¹¹¹Cd atom)=?1.106(4) · 10^?3. This yields an atomic reference scale for all measured NMR line shifts in the liquid and solid state and the possibility of comparing experimental and theoretical shielding constants. As a consequence, the amount of the Knight shift of metallic cadmium becomes 20% larger.     

Crystal structure,NMR spectroscopy,electrical properties of catena-poly[(bis-glycinium-k 2 O:O)-di-μ-thiocyanate- k 2 N:S; k 2 S:N -cadmium (II)]

The crystal structure, the ¹¹¹Cd and ¹³C NMR spectroscopy, and the complex impedance have been carried out on a new polymeric hybrid compound: [Cd(NH₃CH₂COO)₂(SCN)₂] _n . Crystal structure shows that in the title compound the cadmium atoms have a 2N2S2O-hexa-coordination sphere, exhibiting pseudo-octahedral geometry. The cadmium atoms are bridged by two thiocyanate ions generating 1D polymeric chains. ¹¹¹Cd and ¹³C MAS NMR spectroscopy show multiplets that result from ¹¹¹Cd, ¹⁴N and ¹³C, ¹⁴N spin–spin coupling, respectively. The AC impedance measurements were performed as a function of both frequency and temperature. The AC and DC electrical conduction have been studied. The activation energy associated with the bulk resistance determined from equivalent circuit was found close to that of the activation energy obtained from DC conductivity. The conduction mechanisms are attributed to the correlated barrier hopping model.     

Supertransferred hyperfine magnetic fields at111Cd(←111In) in ferrimagnetic oxides with the spinel structure

The supertransferred hyperfine magnetic fields,H _STHF, at¹¹¹Cd(¹¹¹In) on the tetrahedral sites of the spinel oxides Fe_3-xM_xO₄ (M = Ni or Co) were measured by means of the time differential perturbed angular correlation. The observedH _STHF were analyzed as the sum of the fields transferred from individual B site magnetic ions: 11 kOe/Fe³⁺, 8 kOe/Fe²⁺, 4 kOe/Ni²⁺ and 4 kOe/Co²⁺. A brief discussion is presented on these results in comparison with previous ones onH _STHF at¹¹¹Cd(^111mCd) in rocksalt-type oxides and the one at¹¹¹in in NiFe₂O₄.     

Electric quadrupole interaction at 111Cd and 119Sn in isostructural NiIn and CoSn compounds

The perturbed angular correlation technique and Mössbauer spectroscopy were applied to study the electric field gradient on ¹¹¹Cd and ¹¹⁹Sn probe atoms in isostructural NiIn and CoSn compounds. The ¹¹¹Cd PAC measurements performed in the temperature range 80--1100 K demonstrated the existence of two axially symmetric EFG's in each of the investigated compounds, related to the 2(d) and 1(a) probe sites in the B35 structure. A 1(a)-site preference for Cd probes in CoSn compound was observed. The temperature dependence of the quadrupole frequencies for ¹¹¹Cd in both compounds, interpreted in terms of the empirical model proposed by Christiansen et al.[1], follows a T^3/2 relation with different slope parameters for each of the observed frequencies. These results are combined with the data from the Mössbauer experiment. The ¹¹⁹Sn Mössbauer spectra taken at liquid nitrogen and at room temperatures showed two quadrupole split doublets with the intensity ratio 2:1 for CoSn and 8:1 for NiIn_0.99Sn_0.01sample, giving an evidence of 2(d)-site preference for tin atoms in NiIn. The EFG values measured on ¹¹⁹Sn are 2.5 to 4 times larger than those on ¹¹¹Cd nuclei, while the ratio of the respective Sternheimer antishielding factors is equal to 0.77. Within the limits of errors no differences were observed in the magnitude and temperature dependence of Debye--Waller factors for 2(d) and 1(a) ¹¹⁹Sn positions in CoSn and NiIn lattices.     

Semiconductors with structurally determined vacancies – PAC studies

Ternary semiconductors of type □A^IIB ₂ ^III C ₄ ^VI with an ordered array of vacancies were investigated by PAC. Thereby the six probes ¹¹¹Cd, ¹¹⁷Cd(¹¹⁷In), ¹¹¹In(¹¹¹Cd), ¹¹¹Ag(¹¹¹Cd), ⁷⁷Br(⁷⁷Se) and ⁷⁷Kr(⁷⁷Br) were applied. The positions of the different probes are determined and the corresponding electric field gradients by the WIEN 95 code calculated. By ¹¹¹Ag(¹¹¹Cd)-probes the vacancies could be substituted. The electronic charge density distributions are discussed. At elevated temperatures the substances show order–disorder transitions. As compared to the X-ray diffraction patterns the beginning of disorder is observed by PAC at distinctly lower temperatures. This revised version was published online in August 2006 with corrections to the Cover Date.     

Sign of the electric field gradient at111Cd in Zr and Sb

The Β-γ TDPAC technique was applied to¹¹¹Ag implanted in Zr and Sb metal single crystals in order to determine sign and magnitude of the quadrupole interaction at the site of¹¹¹Cd in these metals. An analysis of the data taken at 293K yielded Ν_Q=+15.4(6) MHz for¹¹¹Cd in Zr and Ν_Q=?107.5(20) MHz for¹¹¹Cd in Sb. From these values electric field gradients of +7.3(8)×10¹⁶ V/cm² and ?5.56(62)×10¹⁷ V/cm² for Cd in Zr and Sb are derived respectively.     

The quadrupole moments of Cd and Zn isotopes - an apology

In 2010 we presented an update of the nuclear quadrupole moments (Q) for the Cd and Zn isotopes, based essentially on straightforward density functional (DF) calculations (H. Haas and J.G. Correia, Hyperfine Interact 198, 133–137 (2010)). It has been apparent for some years that the standard DF procedure obviously fails, however, to reproduce the known electric-field gradient (EFG) for various systems, typical cases being Cu₂O, As and Sb, and the solid halogens. Recently a cure for this deficiency has been found in the hybrid DF technique. This method is now applied to solid Cd and Zn, and the resultant quadrupole moments are about 15 % smaller than in our earlier report. Also nuclear systematics, using the recently revised values of Q for the long-lived 11/2 isomers in¹¹¹Cd to¹²⁹Cd, together with earlier PAD data for^107,109Cd, leads to the same conclusion. In addition, EFG calculations for the cadmium dimethyl molecule further support the new values: Q(¹¹¹Cd, 5/2⁺) = .683(20) b, Q(⁶⁷Zn, gs) = .132(5) b. This implies, that the value for the atomic EFG in the \(^{3}\textit {P}_{1}\) state of Zn must be revised, as it has been for Cd.     

Hyperfine interactions at R and In sites in RNiIn (R = Gd, Tb, Dy, Ho) compounds measured by perturbed angular correlation spectroscopy

Perturbed gamma–gamma angular correlation (PAC) technique was used to measure the magnetic hyperfine field (mhf) in RNiIn (R = Gd, Dy, Tb, Ho) intermetallic compounds using the ¹¹¹In→¹¹¹Cd and ¹⁴⁰La→¹⁴⁰Ce probe nuclei. The PAC spectra for ¹¹¹Cd measured above magnetic transition temperature show a major fraction with a well defined quadrupole interaction for all compounds except GdNiIn where a single frequency was observed. PAC measurements below T _C showed a combined electric quadrupole plus magnetic dipole interaction for ¹¹¹Cd probe at In sites, and a pure magnetic interaction for ¹⁴⁰Ce at R sites. The temperature dependence of mhf measured with ¹⁴⁰Ce at R sites shows that the values of fields drop to zero at temperatures around the expected T _C for each compound. However, in the measurements with ¹¹¹Cd at In sites, the mhf values become zero at temperatures which are smaller than T _C . The difference between the temperatures at which mhf is zero for ¹⁴⁰Ce and ¹¹¹Cd probes correlates with T _C . For each compound this difference decreases with T _C . The results are discussed in terms of the RKKY model for magnetic interactions and the existence of two magnetic systems, with distinct exchange interaction energies due to different types of atomic layers in these compounds.     

Quadrupole interaction at111Cd in RRh3B2 compounds (R=Ce to Gd) and absence of transferred hyperfine field at111Cd in GdRh3B2

The quadrupole interaction at¹¹¹Cd in RRh₃B₂ compounds studied by the TDPAC technique supports the prediction that Ce in CeRh₃B₂ is not trivalent. The highly anisotropic EFG indicates that¹¹¹Cd in GdRh₃B₂ cannot occupy the rare earth site. The transferred magnetic hyperfine field at¹¹¹Cd is nearly zero which supports the conjecture that the impurity probe nuclei are at the 3g(Rh) site.     

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.     

The electric field gradient at111Cd in vanadium oxides

The electric field gradient (efg) of¹¹¹Cd in polycrystalline V₂O₅ was studied using perturbed angular correlation (PAC) spectroscopy, with the¹¹¹In activity ion-implanted at 400 keV. Between the individual steps of an isochronal annealing program, a distinct efg (v _Q 1=88.1(3) MHz, ₁=0.62(2)) was recorded the contribution of which increased with annealing temperature up to 74% at 870 K. Corresponding X-ray analysis of inactive V₂O₅ samples, which underwent the same annealing treatment, proved that the sample always stayed as V₂O₅. Since V₂O₅ has only one equivalent cation site, it is concluded that this efg belongs to¹¹¹Cd at this site. Oxidation of a vanadium foil atT=675 and 800 K at =200 mbar also yielded this efg. From PAC measurements in VO₂, two well-defined efg's were found above and below the metal-semiconductor transition at 340 K, which are tentatively attributed to the monoclinic and the tetragonal phase.Supported by Deutsche Forschungsgemeinschaft and DAAD.On leave from the University of Durban-Westville, South Africa.     

Doping of sapphire single crystals with 111In and 111Cd detected by perturbed angular correlation

The electric hyperfine interaction of ion beam implanted ¹¹¹In and ¹¹¹Cd probe atoms in sapphire (Al₂O₃) single crystals has been investigated using perturbed angular correlation spectroscopy. For both probe atoms the same distinctive electric field gradient was found, indicating that nearly all the implanted probe atoms form a stable substitutional configuration in the temperature range between 77 K and 873 K on the aluminum sublattice. A comparative study between ¹¹¹In and ¹¹¹Cd-measurements points to a dynamic interaction initiated by the electron-capture of ¹¹¹In(EC)¹¹¹Cd similar to In₂O₃ and La₂O₃. Size and orientation of the EFG are discussed in comparison to experimental results in Cr₂O₃ single crystals. This revised version was published online in August 2006 with corrections to the Cover Date.     

Deexcitation of Cd 53P1 atoms in collisions with ground state atoms and molecules

Collisions of excited Cd 5³P₁ atoms were investigated using atomic fluorescence spectroscopy. Cadmium vapor, together with a quenching gas, was irradiated in a quartz fluorescence vessel with Cd 3261 Å resonance radiation and the intensity of the resulting resonance fluorescence was monitored in relation to the gas pressures. The experiments yielded the following cross sections Q₁₀ (in A²) for collisional transfer 5³P₁→5³P₀: CdAr=2×10^?3, CdN₂=8.0, CdH₂=7.0, CdCO=15.6. The cross sections Q for collisional deexcitation to the ground state (quenching) in A² are CdN₂ = 2.6×10^?2, CdH₂ = 11.0, CdCO = 3.4, CdCO₂ = 26.