Hyperfine interactions in 111Cd-doped lutetium sesquioxide

We report here first Perturbed Angular Correlation (PAC) results of the electric field gradient (EFG) characterisation at ¹¹¹Cd impurities located at both non-equivalent cation sites of the bixbyite structure of Lutetium sesquioxide, between room temperature (RT) and 1273 K. The comparison with results coming from a systematic ¹¹¹Cd PAC study in bixbyites and with point-charge model (PCM) predictions shows the presence of a trapped defect at RT in the neighbourhood of the asymmetric cation site, which is completely removed at T > 623 K. The anomalous EFG temperature dependence in Lu₂O₃ can be described in the frame of a “two-state” model with fluctuating interactions, which enables the experimental determination of the acceptor energy level introduced by the Cd impurity in the band-gap of the semiconductor and the estimation of the oxygen vacancy density in the sample. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hyperfine Interactions in CeT2Ge2 (T = Mn,Co) Heavy Fermions Compounds Measured by TDPAC

Time Differential Perturbed γ–γ Angular Correlation (TDPAC) technique was used to measure the magnetic hyperfine field at both Ge and Ce sites in CeMn₂Ge₂ and CeCo₂Ge₂ intermetallic compounds. The ¹¹¹In (¹¹¹Cd) probe nuclei was used to investigate the hyperfine interaction at Ge sites, while the ¹⁴⁰La (¹⁴⁰Ce) nuclei was used to measure the magnetic hyperfine field at Ce site. The present measurements cover the temperature ranges from 10–460 K for CeMn₂Ge₂ and 9–295 K for CeCo₂Ge₂, respectively. The result for ¹¹¹Cd probe showed two distinct electric quadrupole frequencies above magnetic transition temperatures, in both compounds and a combined interaction in the magnetic region. The temperature dependence of the magnetic hyperfine field at ¹¹¹Cd at Mn site for the CeMn₂Ge₂ compound showed a transition from ferromagnetic to antiferromagnetic phase around 320 K and from antiferromagnetic to paramagnetic phase at 420 K. While a small magnetic field was measured on ¹¹¹Cd at Co site, no magnetic field on ¹⁴⁰Ce site was observed in CeCo₂Ge₂. This revised version was published online in September 2006 with corrections to the Cover Date.     

Fe-Hydroxysulphates from Bacterial Fe2+ Oxidation

The perturbed angular correlation method (PAC) was applied to investigate the lattice location of implanted ¹¹¹In probe ions in Hf₂Ni and Zr₂Ni intermetallic compounds. It is concluded that the ¹¹¹In/¹¹¹Cd probe nuclei experiencing the highly asymmetric electric field gradient (EFG) occupy the unique hafnium or zirconium 8(h) sites in the investigated phases. Above room temperature, the EFGs decrease linearly with temperature. The results are compared with that of previous PAC measurements with ¹⁸¹Ta probes.     

Precision PAC measurements in Er2O3 and Ho2O3 single crystals and structure refinement

The structure of C-form Ho₂O₃ and Er₂O₃ single crystals and powder samples was investigated by the electric quadrupole hyperfine interaction of¹¹¹In(EC)¹¹¹Cd probe ions using the perturbed - angular correlation method (PAC). The resulting set of refined atomic coordinates is compared to X-ray data and used to calculate the orientations of the electric field gradients (EFG) which are reproduced by the PAC measurements in single crystals. The temperature dependence of the coordinates was measured for both substances.     

Mössbauer Studies on Nanocrystalline Diol Capped γ-Fe2O3

Nanocrystalline indium (nano-In) was prepared with different particle sizes by electrochemical deposition. The temperature dependence of the local electric field gradient (EFG) of nano-In was investigated in a temperature range of 20–300 K using the probe ¹¹¹In for perturbed γγ angular correlation (PAC) experiments. The temperature dependence of the EFG of nano-In can be described by a (1−BT ^3/2) dependence as in bulk-In. It is shown that the low temperature value of the EFG and the proportionality constant B vary systematically with particle size.     

Investigation of spin transition in GdCoO3 by measuring the electric field gradient at Co sites

In the present work, the time differential perturbed angular correlation (PAC) technique was used to study the temperature dependence of electric field gradient (efg) in GdCoO₃ perovskite using ¹¹¹Cd and ¹⁸¹Ta nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced in the oxide lattice through chemical process during sample preparation and were found to occupy only the Co sites in GdCoO₃. The efg's at ¹¹¹Cd and ¹⁸¹Ta show temperature dependence with two different fractions each that change with temperature. In the case of ¹¹¹Cd the quadrupole frequency slowly decreases, with corresponding increase of the temperature and shows a peak like structure at around 200 K and a discontinuity at 700 K. These changes have been interpreted as thermally activated spin-state transitions from low-spin ground state configuration to the intermediate-spin state and from intermediate-spin to high-spin state of Co³⁺${\mathrm{Co}}^{3+}$ ion similar to LaCoO₃ compound. Indication of a Jahn–Teller distortion, which stabilizes the intermediate-spin state with orbital ordering, is also pointed out.     

Temperature dependence studies of the EFG at111Cd probes located in some intermetallic compounds

The temperature dependences of the electric field gradient (EFG) at¹¹¹Cd probes in nickel-indium and indium-tellurium intermetallic compounds have been studied by means of the time differential perturbed angular correlation of gamma rays (TDPAC). The room temperature interaction frequencies (e ² Qq/h) in each case were determined as In₂Te₅ (136 MHz), Ni₃In (13.8 MHz), NiIn (252 and 337 MHz) (two sites), and Ni₂In₃ (162 and 266 MHz) (two sites). The TDPAC pattern of¹¹¹Cd in NiIn did not agree with the previous assignment of the crystal structure. A general discussion of the results related to other temperature dependence studies of the EFG is presented and a general trend is discerned.Supported in part by the US Energy and Research Development Administration.     

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.     

Pressure and temperature dependence of the electric field gradient (EFG) in CdS

Using the time differential perturbed angular correlation technique (TDPAC), the electric hyperfine interaction of¹¹¹Cd in the II-VI-semiconductor CdS was investigated. The results of the temperature and pressure dependence of the electric field gradient (EFG) are discussed. The binding energyE _b for¹¹¹In at a Cd lattice site and a Cd vacancy (¹¹¹In_Cd–V_Cd–pair) could be estimated to 340 meV±80 meV by means of an Arrhenius-Plot. The disappearance of the 79 MHz and 73 MHz frequencies under a pressure of about 30 kbar could be due to their vacancy character or to the beginning of the phase transition to rocksalt structure.     

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.     

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.     

Pressure dependence of the electric field gradient in the AgIn2 intermetallic compound

The pressure dependence of the electric field gradient (EFG) in the AgIn₂ intermetallic compound was measured from zero up to 35 kbar using the time differential perturbed angular correlation technique in¹¹¹Cd. The unit cell volume and thec/a ratio variations with pressure were measured up to 80 kbar. The temperature dependence of the cell parameters was also measured, in a range varying from 300 K up to 458 K. The relationship of these results showed that the contribution of the lattice thermal expansion to the EFG variations is about 1/3, a small but not negligible part. The estimated EFG volumetric dependence is at variance with the systematic results found in pure metals. Work supported in part by FINEP and CNPq (Brasil).     

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.     

Investigation of hyperfine interactions in GdCrO3 perovskite oxide using PAC spectroscopy

Perturbed angular correlation (PAC) measurements have been carried out in the antiferromagnetic GdCrO₃ perovskite oxide using ¹¹¹In (¹¹¹Cd) and ¹⁸¹Hf(¹⁸¹Ta) nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced in the compound through a chemical process during sample preparation. The PAC measurements were carried out in the temperature range 20–300 K. Measurements with the ¹⁸¹Ta indicated a unique quadrupole interaction above 170 K and a combined electric quadrupole and magnetic dipole interactions below this temperature. The observed interaction was assigned to the probe nuclei substituting Cr sites. Measurements with ¹¹¹Cd showed two quadrupole interactions. Only one of the fractions however, showed a combined electric and magnetic interaction in the temperature rage 20–170 K which was assigned to ¹¹¹Cd probe substituting Cr site. The other fraction was attributed to the Gd site. The present results are compared with those of LaCrO₃ and NdCrO₃.     

Pressure dependence of the electric field gradient in Sb and Sb1−x M x (M=ln,Zn, Ge,Pb, Cd,Sn) at the site of111Cd

Using the¹¹¹Cd-TDPAC (time differential perturbated angular correlation) method, the pressure dependence of the electric field gradient (EFG) in Sb and Sb_1–x M _x (M=ln, Zn, Ge, Pb, Cd, Sn) was investigated. The application of a phenomenological ansatz for the parametrisation of the pressure and temperature dependence of the EFG made it possible to combine temperature data gained in former studies [1], [2] with the pressure dependent data presented in this paper. The resulting pressure dependence of –2±0.2 MHz/kbar is shown to be independent of concentration and element of admixture. Results for the volume and explicit temperature dependence agree with existing information on the mixed system Sb_1–x M _x (M=ln, Zn, Ge, Pb, Cd, Sn); the investigation of the EFG in Sb_1–x–y M _x Pb _y showed that the resulting EFG may be interpreted as the weighted sum of the individual contributions of the two metals.This paper is dedicated to Prof. Dr. W. Kreische on the occasion of his 60th aniversary on 02.02.1995     

Temperature dependence of electric field gradient in TbCoO3

The temperature dependence of the electric field gradient (efg) in TbCoO₃ perovskite was measured by perturbed angular correlation (PAC) technique using ¹¹¹Cd and¹⁸¹Ta nuclear probes. The radioactive parent nuclei ¹¹¹In and ¹⁸¹Hf were introduced into the compound through a chemical process during sample preparation. The electric quadrupole interactions at ¹¹¹Cd show two different sites, assigned to probe substituting Tb and Co atoms. The temperature dependence of quadrupole frequencies show sharp discontinuities which have been interpreted as thermally activated spin state transitions from low-spin ground state configuration to the intermediate-spin state and from intermediate-spin to high-spin state of Co^3?+? ion. For ¹⁸¹Ta only one interaction was observed, which was assigned to probe at Co site. Indication of a Jahn–Teller distortion, which stabilizes the intermediate-spin state with orbital ordering, is also pointed out. No magnetic order was observed till 77 K.     

Hyperfine spectroscopic study of the metal-insulator transition in V2O3

The metal-insulator (M-I) transition in vanadium sesquioxide V₂O₃ has been investigated by time differential perturbed angular correlation measurements of the electric fieldgradient (EFG) and the magnetic hyperfine field at dilute¹¹¹Cd impurities. The EFG undergoes a first-order change at the M-I transition at T_t=160 K, but does not reflect the high temperature resistivity anomaly. The increase of the EFG with temperature in the metallic phase can be attributed to thermal variations of the oxygen sublattice. The temperature dependence of the magnetic hyperfine field in the insulating phase follows a Brioullin function with a saturation value of H_hf(O)=15 KOe and an extrapolated Neel temperature, which, depending on the impurity concentration, varies between 188 and 230 K.     

PAC measurements in titanium and titanium-hydrogen alloys

Measurements have been performed with the PAC method in pure hcp titanium and highly concentrated titanium hydrogen alloys to investigate the temperature dependence of the electric field gradient (EFG) in both systems. In pure titanium it can be explained by a recent theoretical model; in the titanium hydride the EFG reveals a strong decrease with temperature, which indicates enhanced local vibration amplitudes. Furthermore the interaction of hydrogen and oxygen impurities with the¹¹¹In probe atoms have been studied.     

Dynamic hyperfine interactions in In(Cd)-doped ZnO semiconductor: PAC results supported by ab initio calculations

In this work, we present results of Time-Differential γ–γ Perturbed-Angular-Correlations (PAC) experiments performed in ¹¹¹Cd-doped ZnO semiconductor. The PAC technique has been applied in order to characterize the electric-field-gradient (EFG) tensor at (¹¹¹In (EC)→) ¹¹¹Cd nuclei located, as was later demonstrated, at defect-free cation sites of the ZnO host structure. The PAC experiments were performed in the temperature range of 77–1075 K. At first glance, the unexpected presence of low-intensity dynamic hyperfine interactions was observed, which were analyzed with a perturbation factor based on the Bäverstam and Othaz model. The experimental EFG results were compared with ab initio calculations performed with the Full-Potential Augmented Plane Wave plus local orbital (FP-APW+lo) method, in the framework of the Density Functional Theory (DFT), using the Wien2K code. The presence of the dynamic hyperfine interactions has been analyzed enlightened by the FP-APW+lo calculations of the EFG performed as a function of the charge state of the cell. We could correlate the large strength of the dynamic hyperfine interaction with the strong variation of the EFG due to changes in the electronic charge distribution in the Cd vicinity during the time-window of the PAC measurement. It was also revealed that the Cd impurity decays to a final stable neutral charge state (Cd²⁺) fast enough (in few ns) to produce the nearly undamped observed PAC spectra.