Study of the23Na EFG tensor as determined from first order NMR satellite lines near the ferroelectric phase transition of AgNa(NO2)2

The²³Na NMR first order quadrupolar satellite lines are detected and studied in AgNa(NO₂)₂ single crystals near the paraelectric-ferroelectric phase transition. Although the intensities of the satellites are small the components of the electric field gradient tensor (EFG) at the²³Na sites could be deduced from the angular dependence of the first order quadrupolar line splitting with respect to rotations around the three crystallographic axes by applying the Volkoff method. In the paraelectric phase the principal axes system of the EFG coincides with the crystallographic axes system whereas in the ferroelectric phase there is a strongly temperature dependent small non diagonal element _xz (T). The EFG principal components _xx and _yy are strongly influenced whereas the EFG principal component _zz is nearly not affected by the ferroelectric phase transition. The observed temperature dependences of the EFG components are related to the temperature variation of the normalized spontaneous polarizationS(T) by assuming a coupling term which is quadratic inS(T). Finally the problem of the intensities of the satellite lines is 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.     

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.     

Martensitic phase transition due to soft phonon mode in β′ phase alloys

The soft phonon modes relating to the martensitic phase transition in the β′ alloys are analysed by group- theoretical methods. The characteristic of the transition in the O⁵_h type β′ alloy are different from that of the O¹_h type one.     

Nuclear acoustic resonance of V51 in a single crystal of V3Si above and below the martensitic transformation

The EFG and the Knight shift anisotropy of V⁵¹ in a single crystal of V³Si have been measured both above and below the martensitic transformation temperature T_m, using the nuclear acoustic resonance technique. Deviations of the axial symmetry of the EFG tensor have been found below T_m. The orientation of the tetragonal c axis in the crystal is also given.     

Nonempirical cluster calculations of the electric field gradient tensor in yttrium-aluminum garnet Y3Al5O12

The electric field gradient (EFG) tensor at the aluminum nucleus sites in yttrium-aluminum garnet Y₃Al₅O₁₂ is calculated using the Hartree-Fock method and the nonempirical cluster approach. It is shown that the EFG tensor at the Al_tetr sites is described well taking into account the nearest neighbors (an [AlO₄]^?5 cluster), whereas for the Al_oct sites the effect of more distant ions is important. The results are compared with the available experimental data and the results of band calculations.     

Untersuchungen der Struktur von „antiferroelektrischem”(NH4)2H3IO6 mit Kernresonanzmethoden

The orientations and asymmetry parameters of the EFG tensors at the different lattice sites of I¹²⁷ in (NH₄)₂H₃IO₆ have been determined by proton-iodine crossover relaxation at room temperature and at 94°K. Based on these results it was possible to prove the existence of superstructure for the hexagonala- andc-directions and to reduce the number of allowed space groups of the low temperature phase to two: \(R\overline 3 c\) andR32. In both space groups half of the hydrogen bonds remain symmetric and only half of them become asymmetric (ordered) on lowering the temperature through the phase transition, but only inR32 there are antipolar sublattices. The transition entropies calculated for this model of the hydrogen arrangement agree fairly well with the measured value. With the evidence available it is not possible to rule out one of the two space groups.     

Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds

Two hexanuclear niobium halide cluster compounds with a [Nb₆X₁₂]²⁺ (X=Cl, Br) diamagnetic cluster core, have been studied by a combination of experimental solid-state NMR/NQR techniques and PAW/GIPAW calculations. For niobium sites the NMR parameters were determined by using variable B_o field static broadband NMR measurements and additional NQR measurements. It was found that they possess large positive chemical shifts, contrary to majority of niobium compounds studied so far by solid-state NMR, but in accordance with chemical shifts of ⁹⁵Mo nuclei in structurally related compounds containing [Mo₆Br₈]⁴⁺ cluster cores. Experimentally determined δ_iso(⁹³Nb) values are in the range from 2400 to 3000 ppm. A detailed analysis of geometrical relations between computed electric field gradient (EFG) and chemical shift (CS) tensors with respect to structural features of cluster units was carried out. These tensors on niobium sites are almost axially symmetric with parallel orientation of the largest EFG and the smallest CS principal axes (V_zz and δ₃₃) coinciding with the molecular four-fold axis of the [Nb₆X₁₂]²⁺ unit. Bridging halogen sites are characterized by large asymmetry of EFG and CS tensors, the largest EFG principal axis (V_zz) is perpendicular to the X-Nb bonds, while intermediate EFG principal axis (V_yy) and the largest CS principal axis (δ₁₁) are oriented in the radial direction with respect to the center of the cluster unit. For more symmetrical bromide compound the PAW predictions for EFG parameters are in better correspondence with the NMR/NQR measurements than in the less symmetrical chlorine compound. Theoretically predicted NMR parameters of bridging halogen sites were checked by ^79/81Br NQR and ³⁵Cl solid-state NMR measurements.     

Electric field gradients in Hf2Fe

Perturbed Angular Correlations (PAC) technique was applied to measure the electric field gradients (EFG) at ¹⁸¹Ta sites in Hf₂Fe. The compound has the cubic structure of the Ti₂Ni prototype with two non‐equivalent crystallographic sites for Hf atoms. EFGs for the two sites were measured as a function of the temperature. In addition, one more EFG was observed, which was assigned to the presence of defects in the lattice. The ratio of the measured EFG at the regular lattice sites has been used to assign charges to the ions through a simple calculation using the point charge model and it is shown that the lattice symmetry can explain the very different EFG at both sites. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hyperfine interactions measurements on 181Ta probes in HfV2Hx compounds: (0⩽x≲4)

The electric field gradient (EFG) has been measured on ¹⁸¹Ta probe sites in HfV₂H_x alloys (0?x?4) using the time differential perturbed angular correlation technique. One observes that the main component V_zz of the EFG decreases by a factor of 2 for hydrogen concentrations increasing from x = 0 to x = 4 hydrogen atoms/formula. The opposite behavior was observed on ⁵¹V by using the NMR technique. At T = 4.2 K the EFG tensor is non-axially symmetric. The observed asymmetry factor for x = 0 is η = 0.58(3) and it slightly increases to η = 0.70 for x?4. The system is orthorhombic at low temperatures for all x and the experiments suggest that hydrogen would stabilize a tetragonal phase at higher temperatures. The relaxation effects are absent for x = 0 and vanishingly small for x ? 4 but they are observed at intermediate concentrations supporting the idea of a hydrogen ordering for x = 4.     

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.     

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     

TDPAC study of amorphous alloys Pd0.8Si0.2 and Pd0.75Si0.20Ag0.05

The amorphous alloys Pd_0.8Si_0.2 and Pd_0.75Si_0.20Ag_0.05 have been studied by the time differential perturbed angular correlation method. A broad EFG distribution with a relative width of 0.48–0.51 was sensed by the probe nuclei¹¹¹Cd for both the amorphous alloys. The unique quadrupole interaction frequencies were observed after annealing above the phase transition temperature. The observed broad distribution of the EFG implies that the crystallographic structure of the amorphous alloys is characterized by short-range order and long-range disorder, which is in accord with the continuous random model.     

Large successive magnetocaloric effects around room temperature in Ni<Subscript>50</Subscript>Mn<Subscript>34</Subscript>In<Subscript>15</Subscript>Al alloy

Two successive magnetocaloric effects consisting of inverse magnetocaloric effect around martensitic transition and negative magnetocaloric effect around magnetic transition of austenitic phase have been observed in Ni₅₀Mn₃₄In₁₅Al alloy. Large inverse magnetic entropy change ΔS_m ( ~ 21.3 J kg^?1 K^?1), small thermal and magnetic hysteresis of martensitic transition give rise of large net refrigerant capacity ( ~ 152.3 J kg^?1) under a magnetic field of 50 kOe, which is comparable with that ( ~ 157.9 J kg^?1) of second-order transition. The large combined magnetocaloric effects make the Ni₅₀Mn₃₄In₁₅Al alloy as a promising candidate material for room temperature magnetic refrigeration.     

Study of highT c superconductivity in Y1Ba2Cu3O7−x by PAC

HighT _c superconductivity in the YBaCuO superconductor has been investigated through the quadrupole interaction of the probe nuclei⁹⁹Tc. The quadrupole interactions were measured by the TDPAC method from 77 to 296 K. The probe nuclei⁹⁹Tc were introduced into the YBaCuO superconducting specimen by diffusion. The derived electric quadrupole interaction parameters show that the probe nuclei are subject to a unique EFG interaction and occupy a substitutional lattice site in the YBaCuO superconductor. A strong EFG of 10¹⁹ V/cm² was observed. The temperature dependence of the EFG exhibits a linear decrease with temperature increase. Anomalies of both EFG and ν were found in the superconducting transition temperature region. The role of the oxygen vacancies in the Cu−O chains is discussed.     

Phase transition in Cu2+-doped RbH2 PO4 as observed by EPR

The electron paramagnetic resonance (EPR) spectra of Cu²⁺-doped RbH₂ PO₄ at elevated temperatures indicate a phase transition at 358 K. The EPR-silent state at this temperature is attributed to a so-called polymeric phase transition. After the transition when the temperature is lowered to 293 K, the EPR signal does not appear; therefore, the transition is irreversible. This result seems to be in agreement with the other observations. The EPR spectra for the sample indicate the presence of two sites for Cu²⁺, and the values of EPR parameters are in accord with the literature on Cu²⁺-doped single crystals. Any other phase transitions could not to be observed at low temperatures down to 113 K.     

On the Mössbauer site assignment in YBa2(Cu1−xFex)3Oy

The assignment of the four⁵⁷Fe Mössbauer sites which are observed in Fe-substituted YBa₂Cu₃O_y is presented. We present a systematic study of highly-controlled samples with low Fe-concentration over the whole oxygen concentration range. Two sites are found to dominate in the limit of high oxidation (y→7), indentified as Fe⁴⁺ on the two crystallographic Cu sites: Cu(1) and Cu(2). These are replaced at lower oxidation (y→6) by two others, which we identify with Fe³⁺ on these same two sites. Consistency is found with the sign of the electric field gradient (EFG), the asymmetry parameter η and the isomer shiftI _S for this model. The magnetic structure in the limit y→6 shows changes in the antiferromagnetic (AF) structure dependent on iron concentration. Mössbauer and spin-echo NMR results show a change in the Cu(2) AF layer sequence at low temperatures, without any magnetic moments on the Cu(1) chain sites.     

Influence of the martensitic structure transformation in LaAg x In1−x on the magnetic properties of substituted Ce

The martensitic phase transformation has no observable effect on the magnetic susceptibility of Ce in LaAg _x In_1–x which agrees with the assumption of a crystal field splitting by 300 K of the² F _5/2 ground state of Ce³⁺ ions. The magnetic ordering temperature and the Kondo minimum move to higher temperatures together with the martensitic phase transformation when the Ag concentration is reduced. This behavior can be related qualitatively to the lowering of the 5d – e _g levels in the center of the Brillouin-zone with increasing In content.     

Influence of the martensitic structure transformation in LaAgxIn1?x on the magnetic properties of substituted Ce

The martensitic phase transformation has no observable effect on the magnetic susceptibility of Ce in LaAg _x In_1–x which agrees with the assumption of a crystal field splitting by 300 K of the² F _5/2 ground state of Ce³⁺ ions. The magnetic ordering temperature and the Kondo minimum move to higher temperatures together with the martensitic phase transformation when the Ag concentration is reduced. This behavior can be related qualitatively to the lowering of the 5d – e _g levels in the center of the Brillouin-zone with increasing In content.     

Photoluminescence properties of Sm-doped BaBr2 under hydrostatic pressure

Photoluminescence spectra of Sm²⁺-doped BaBr₂ have been measured under hydrostatic pressures up to 17 GPa at room temperature. In the low pressure range a red-shift of the broad 5d-4f transition of −145 cm⁻¹/GPa is observed. From 5 to 8 GPa a phase mixture of the initial orthorhombic phase and the high-pressure monoclinic phase gives rise to two 5d-4f bands, which are strongly overlapping. Above 8 GPa the crystal is completely transformed to its high-pressure phase where two different Sm²⁺ sites exist, but only one broad 5d-4f transition is detected. It exhibits a red-shift of −36 cm⁻¹/GPa. In addition, the line shifts of the ⁵D₀→⁷F_J (J=0, 1, 2) transitions are investigated. Linear shifts of −19 cm⁻¹/GPa for J=0, 2 and of −13 cm⁻¹/GPa for J=1 are observed in the pressure range from 0 to 5 GPa.