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.     

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.     

The quadrupole interaction at181Ta in Zn

The quadrupole interaction (QI) in hexagonal close packed zinc lattice was measured using the 482 keV, 10.6 ns probe state of¹⁸¹Ta employing the time-differential perturbed angular correlation technique. The electric field gradient (EFG) at¹⁸¹Ta in Zn was derived from the measured quadrupole interaction frequency at room temperature asV _zz =12.202×10¹⁷ V/cm². The quadrupole interaction measured at various temperatures displayed normal temperature dependence similar to that seen by this probe in many non-cubic hosts.     

Hf3Al2 and Zr3Al2 Isostructural Aluminides Studied by PAC with 181Ta and 111Cd Probes

The electric quadrupole hyperfine interactions for ¹⁸¹Hf/¹⁸¹Ta and for ¹¹¹In/¹¹¹Cd probes in polycrystalline Zr₃Al₂ and Hf₃Al₂ compounds were measured in the temperature range 24–1100 K. The hyperfine quadrupole interaction parameters were determined after different doping techniques and heat treatments of the samples.¹⁸¹Hf/¹⁸¹Ta was found to substitute the Hf/Zr sites and the ¹¹¹In/¹¹¹Cd impurities appear to substitute both the 8(j) Al sites and the three nonequivalent Hf/Zr sites.     

Momentum dependence of spin polarization for beta emitting nuclei produced through charge exchange reaction at intermediate energy

Hyperfine interactions were studied in the intermetallic compound GdRh₂Si₂ by perturbed angular correlation (PAC) technique using ¹⁸¹Hf(¹⁸¹Ta) probe nuclei. The measurements were performed in the temperature range 15–285 K. The PAC spectra above the antiferromagnetic ordering temperature of the GdRh₂Si₂ compound (T _N ～ 106 K), were analyzed using a model that included only electric quadrupole interactions. The observed major fraction was assigned to the ¹⁸¹Hf(¹⁸¹Ta) probe substituting the Gd atoms. The PAC spectra below Néel temperature were analyzed using combined electric quadrupole and magnetic dipole interactions. The B_hf value at Gd, measured at 15 K was found to be 1.4(1) T which, is smaller, when compared with the values obtained in this compound using other nuclear probes, ¹⁵⁵Gd (B_hf ～ 30 T) and ¹⁴⁰Ce (B_hf ～ 26 T). The present result using ¹⁸¹Hf(¹⁸¹Ta) probe is quite interesting since it shows that the contribution to B_hf at Gd due the host is smaller than other components which contribute to the hyperfine field. The temperature dependence of B_hf shows an anomalous behavior.     

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.     

The Electric Field Gradients in (Zr/Hf)Al3 and (Zr/Hf)2Al3 Intermetallic Compounds Studied by 181Ta- and 111Cd-PAC Spectroscopy

The electric quadrupole hyperfine interactions for ¹⁸¹Hf/¹⁸¹Ta and for ¹¹¹In/¹¹¹Cd probes in polycrystalline ZrAl₃ and Zr₂Al₃ compounds were measured in the temperature range 30–1100 K and compared with the results for isostructural hafnium aluminides. On the basis of the similarities of the numbers, sizes and asymmetries of electric field gradients, lattice site allocations were made. In all matrices, ¹⁸¹Hf/¹⁸¹Ta was found to substitute the Hf/Zr site. The ¹¹¹In/¹¹¹Cd impurities were also assigned to the Hf/Zr site in the compounds (Zr/Hf)Al₃, but appear to substitute the two non-equivalent Al sites in the Zr₂Al₃ and Hf₂Al₃ phases. This revised version was published online in September 2006 with corrections to the Cover Date.     

Magnetic hyperfine fields at Gd and in sites in GdPdIn compound

Perturbed gamma-gamma angular correlation (PAC) technique was used to measure the hyperfine interactions in the intermetallic compound GdPdIn using ¹¹¹In→ ¹¹¹Cd and ¹⁴⁰La→ ¹⁴⁰Ce probe nuclei at the In and Gd sites, respectively. The PAC results for ¹¹¹Cd show two well-defined electric quadrupole frequencies above T _C assigned to probes occupying Gd and In sites, with ~50% of site occupation each. The fraction corresponding to In sites increases with temperature reaching 95% around 500 K. Below T _C the measurements for ¹¹¹Cd probe showed combined electric quadrupole plus magnetic dipole interaction with sharp increase in the magnetic field below around 80 K. A pure magnetic interaction with lower hyperfine field values was observed at the Gd sites occupied by ¹⁴⁰Ce below 100 K.     

Measurement of Quadrupole Interactions in LaMO3 (M = Cr,Fe, Co) Perovskites by TDPAC

The perturbed angular correlation (PAC) technique has been used to study the electric field gradient (EFG) in LaCoO₃ perovskite. The results are compared with those for LaCrO₃, LaFeO₃ measured earlier. The PAC probe, ¹¹¹In → ¹¹¹Cd, was introduced in the oxide lattice by means of chemical reaction during sample preparation. In the present work, the temperature dependence of the electric quadrupole interaction parameters, for LaCoO₃ was investigated. The resulting systematics of EFG at ¹¹¹Cd, in La(Cr,Fe,Co)O₃ perovskites, reveals a linear dependence with temperature. This revised version was published online in September 2006 with corrections to the Cover Date.     

The electric quadrupole interaction of181Ta in the Hf−As system

The temperature dependence of the electric quadrupole interaction of¹⁸¹Ta in the Hf?As system has been investigated using the time-differential perturbed angular correlation technique. The sample was prepared by thermal diffusion of¹⁸¹Hf into arsenic metal and the measurements were made at 77, 300, 423, 573 and 673 K. Two quadrupole interaction frequencies were observed which had considerably high values and showed little variation over the entire temperature range. A TEM analysis of the sample showed the presence of two intermetallic compounds HfAs and HfAs₂ to which the two frequencies were assigned.     

Electric quadrupole interactions in nano-structured SnO 2 as measured with PAC spectroscopy

Measurements of the electric quadrupole interaction were used to characterize pure and cobalt-doped samples of SnO₂ prepared by the sol-gel method. Perturbed gamma–gamma angular correlation (PAC) spectroscopy using ¹¹¹In–¹¹¹Cd probe nuclei was employed for these measurements. A methodology was developed for sample preparation that were prepared by sol-gel method from pure metallic Sn (99.9999%) and Co (99.9998%) as starting materials. Carrier-free ¹¹¹In was added to the precursor sol-gel solution prior to the formation of gel. PAC measurements were carried out to follow the formation of the SnO₂. PAC measurements were carried out in the temperature range from 10 k to 1123 K and the results show that the electric quadrupole frequency depends on the annealing temperature.     

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.     

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.     

Investigation of Hyperfine Interactions in GdNiIn Compound

Perturbed gamma–gamma angular correlation technique was used to measure the hyperfine interactions in the compound GdNiIn using the ¹¹¹InCd → and ¹⁴⁰La¹⁴⁰Ce probe nuclei at the In and Gd sites, respectively. A unique quadrupole frequency with asymmetry parameter η = 0.78 was observed for ¹¹¹Cd probe at In sites for the measurements above Curie temperature. Below T _C , the spectra for ¹¹¹Cd show combined magnetic dipole and electric quadrupole interaction. Below 85 K, a unique magnetic interaction is observed at ¹⁴⁰Ce. A linear relationship between the saturated magnetic hyperfine field and the magnetic transition temperature was observed for both probes, indicating that the main contribution to the mhf comes from the conduction electron polarization.     

Study of hyperfine interactions in the intermetallic compound CePd2Si2 using PAC technique with 111Cd as probe nuclei

Perturbed γ???γ angular correlation spectroscopy (PAC) has been used to investigate the hyperfine interactions in the intermetallic compound CePd₂Si₂ using ¹¹¹In→¹¹¹Cd probe nuclei. Samples of CePd₂Si₂ were prepared by melting constituent elements in an arc furnace under pure argon atmosphere. Carrier-free ¹¹¹In nuclei were introduced into the samples by thermal diffusion at 800°C in vacuum during 12 h. The measurements were performed in the temperature range of 4.2–300 K. Above the magnetic transition temperature (T _N ?=?10 K), the results show two distinct and well defined quadrupole interactions that were assigned to probe nuclei occupying Ce and Si sites in the compound. The quadrupole frequencies were found to decrease linearly with increasing temperature. The PAC spectra taken below 10 K were analyzed with a model including combined electric quadrupole plus magnetic dipole interactions, from which the hyperfine magnetic field was determined.     

Lattice instability in Hf1-x Ta x V2 compounds

The temperature dependence of the electric quadrupole interaction frequency _l ^o , experienced by the¹⁸¹Ta probe occupying Hf site in the compounds Hf_1-xTa_xV₂ has been measured for x=0.06, 0.10 and 0.20 in the temperature region between 8.5 K to 296 K. The measurements show lattice transformation in all the three compounds below 120 K.     

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.     

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.     

Pac studies of the electric quadrupole interaction of181Ta in yttrium and copper oxides and in super conducting ceramics YBa2Cu3O7−δ

The electric quadrupole interaction of¹⁸¹Ta in Y₂O₃, CuO, and in the YBa₂Cu₃O_7−δ high temperature superconductors, doped with¹⁸¹Hf, has been studied by the time-differential perturbed angular correlation method (TDPAC). In Y₂O₃, two distinct fractions of the probe nuclei were detected, which were attributed to the substitutional positions at the two cation sites in the lattice. In CuO, and in the ceramic samples, broad distributions of quadrupole frequencies were observed. Possible configurations of the probe nuclei in these substances are discussed.     

The Nonanuclear [Mo(IV){(CN)Fe(III)(3-ethoxy-saldptn)}8]Cl4 Complex Compound Exhibits Multiple Spin Transitions Observed by Mössbauer Spectroscopy

The hyperfine interactions at ¹⁸¹Ta ions on Fe³⁺ sites in α-Fe₂O₃ (hematite) were studied in the temperature range 11–1100 K by means of the perturbed angular correlation (PAC) technique. The ¹⁸¹Hf(β⁻)¹⁸¹Ta probe nuclei were introduced chemically into the sample during the preparation. The hyperfine interaction measurements allow to observe the magnetic phase transition and to characterize the supertransferred hyperfine magnetic field B_hf and the electric field gradient (EFG) at the impurity sites. The angles between B_hf and the principal axes of the EFG were determined. The Morin transition was also observed. The results are compared with those of similar experiments carried out using ¹¹¹Cd probe. ^aAlso at Comisión de Investigaciones Científicas de la Provincia de Buenos Aires, Argentina.