NMR in Laves phase alloy system GdPt x —analysis of nonstoichiometry in intermetallic compounds

NMR is applied to ferromagnetic Laves phase compounds Gd_1–x A _x Pt₂ (A=Sc, La) and GdPt _x (2x3). The different hyperfine field contributions are analyzed. Neighbour contributions to the Gd hyperfine field and strength of ferromagnetic coupling are compared. It is found that there is a strong predominance of the nearest neighbour contribution (92%) to the Pt hyperfine field. We show that the Pt NMR allows to derive the deviation in occupation number of Gd atoms on Gd sites in nonstoichiometric compounds with about 4% accuracy.Now with Dürrwächter K. G., Pforzheim     

Deformation change in light iridium nuclei from laser spectroscopy

Laser spectroscopy measurements have been performed on neutron-deficient and stable Ir isotopes using the COMPLIS experimental setup installed at ISOLDE-CERN. The radioactive Ir atoms were obtained from successive decays of a mass-separated Hg beam deposited onto a carbon substrate after deceleration to 1kV and subsequently laser desorbed. A three-color, two-step resonant scheme was used to selectively ionize the desorbed Ir atoms. The hyperfine structure (HFS) and isotope shift (IS) of the first transition of the ionization path 5d ⁷6s ²⁴ F _9/2 → 5d ⁷6s6p ⁶ F _11/2 at 351.5nm were measured for ^182-189Ir, ¹⁸⁶Ir ^m and the stable ^{191, 193}Ir. The nuclear magnetic moments μ_I and the spectroscopic quadrupole moments Q_s were obtained from the HFS spectra and the change of the mean square charge radii from the IS measurements. The sign of μ_I was experimentally determined for the first time for the masses 182≤A≤189 and the isomeric state ¹⁸⁶Ir ^m . The spectroscopic quadrupole moments of ¹⁸²Ir and ¹⁸³Ir were measured also for the first time. A large mean square charge radius change between ¹⁸⁷Ir and ¹⁸⁶Ir ^g and between ¹⁸⁶Ir ^m and ¹⁸⁶Ir ^g was observed corresponding to a sudden increase in deformation: from β₂ ≃ + 0.16 for the heavier group A = 193, 191, 189, 187 and 186m to β₂≥ + 0.2 for the lighter group A = 186g, 185, 184, 183 and 182. These results were analyzed in the framework of a microscopic treatment of an axial rotor plus one or two quasiparticle(s). This sudden deformation change is associated with a change in the proton state that describes the odd-nuclei ground state or that participates in the coupling with the neutron in the odd-odd nuclei. This state is identified with the π3/2⁺[402] orbital for the heavier group and with the π1/2^-[541] orbital stemming from the 1h _9/2 spherical subshell for the lighter group. That last state seems to affect strongly the observed values of the nuclear moments.     

Investigation of the hyperfine interaction of the transition element impurity193Ir in gadolinium

The combined magnetic and electric hyperfine interaction of dilute¹⁹³Ir impurities in ferromagnetic Gd has been investigated by means of the Mössbauer effect. The magnetic hyperfine field of¹⁹³Ir in Gd at 4.2 K is: |H _hf(Ir:Gd)|=624(6) kG.The electric fieldgradient at the site of Ir in Gd is:V _zz (Ir:Gd)=+19.5(5.0) × 10¹⁷ V/cm².The fieldgradient is axially asymmetric with an asymmetry parameter of 0.53(2)1.     

Exchange fields in Gd–Fe intermetallics studied by inelastic neutron scattering

Inelastic neutron scattering (INS) was used to study the magnetic excitations in the compounds Gd_1−xY_xFe₂ and Gd_2−xY_xFe₁₄B. Three inelastic magnetic lines were observed in the INS spectra of these compounds, the two smaller lines appearing as shoulders to the main line. From the concentration-dependent shift of the dominant magnetic line we have obtained experimental information of the strength of the Gd–Gd interaction in these materials and showed that the Gd–Gd contribution to the total molecular field experienced by the Gd moments is roughly an order of magnitude smaller than the contribution of the Gd–Fe interaction. Our results are compared with several earlier published results, including results of electronic band structure calculations.     

The influence of the composition of eight-atom Pt–Ir clusters on the magnetic properties

The energetic stability, electronic structure and magnetic properties of Pt_8–nIr_n clusters have been investigated by employing the spin-polarised generalised gradient approximation. The cubic structure is expected to be the effective building block in Ir-rich clusters after optimisation extensively. The average binding energy of all the clusters presents the linear increment trend with iridium atoms, due to the stronger interaction between Ir atoms than Pt atoms. Bader charge analysis shows how tiny charge transfers from iridium to platinum. The atomic moments of Ir are larger than that of Pt, and the Ir-rich clusters show greater moments than the Pt-rich cluster, with the exception of Ir₈ and Ir₇Pt. A unique magnetic property is found in the Pt₄Ir₄ cluster, where two Pt atoms show antiferromagnetic alignment and the other atoms are found to be aligned ferromagnetically.     

EXAFS study of the local Gd environment in the magnetic superconductor (La1−xGdx)Os2

The near-neighbor environment of Gd in the pseudobinary compound La_1?xGd_xOs₂ has been investigated by studying the EXAFS on the Gd LIII, La LII, and Os LIII edges. For Gd concentrations of x = 0.07 and x = 0.14, we find that the Gd predominantly substitutes on the La sites in the LaOs₂ lattice rather than forming local Gd metal or GdOs₂ clusters. These results are discussed in view of the fact that La_1?xGd_xOs₂ shows spin-glass-like properties (x ≤ 0.15) in the superconducting phase.     

Pressure-Induced Decrease in the Curie Temperature of Gd<Subscript>2</Subscript>Fe<Subscript>17</Subscript>: LSDA+U Calculations

To explain the magnetic properties of advanced ferromagnetic intermetallic compounds of the R₂Fe₁₇ (R is a rare-earth element) class, experimentalists often use the hypothesis of competition between ferromagnetic exchange and antiferromagnetic exchange between four types of the nearest iron atoms in nonequivalent lattice sites. For the rhombohedral Gd₂Fe₁₇ ferromagnet, we calculate the magnetic moments of iron and gadolinium ions, the parameters of exchange between Fe atoms, and Curie temperature T_C at a zero pressure and during hydrostatic lattice compression. The magnetic moment of the unit cell of Gd₂Fe₁₇ is shown to decrease under pressure, and this decrease is almost completely associated with a decrease in the magnetic moments of Fe rather than Gd ions, the pressure dependence of the magnetic moments of which is weaker by an order of magnitude. In contrast to the hypothesis regarding the competition of exchange interactions between different kinds of Fe atoms, the parameters of exchange between the nearest iron atoms in different crystallographic sites are found to be positive ferromagnetic (at a zero pressure and during compression), and a ferromagnetic character of interaction is shown to remain unchanged under pressure even for Fe atoms in the so-called dumbbell sites with the nearest interatomic distances. The Curie temperature T_C of Gd₂Fe₁₇ is shown to decrease with increasing pressure. The changes in the exchange parameters and the magnetic moments of Gd₂Fe₁₇ during compression are found to be mainly related to a change in the position of energy spectrum branches with respect to each other and the Fermi level ?_F rather than to a change in the overlapping of wavefunctions, which play a minor role.     

The magnetic hyperfine field and the electric field gradient at181Ta impurities in Gd metal

The magnetic hyperfine fieldH _hf and the electric field gradientV _zz at¹⁸¹Ta impurties in metallic Gd were determined by time differential perturbed angular correlation measurements with the 133 keV K-conversion electron 482 keV -cascade of¹⁸¹Ta. The sources for these measurements were prepared by implantation of radioactive¹⁸¹Hf ions into Gd. The results are: |H _hf(TaGd; 77 K)|=285(14)kG, and |V _zz(TaGd; 330 K)|=5.32(15)·10¹⁷V/cm². The value ofH _hf fits well into the systematics for 5d impurities in Gd and indicates a positive core polarisation contribution, which is expected if the conduction electrons of Gd have to a large extent d-character. The electric field gradients of the 5d impurities in Gd are not consistent with a proportionality between the ionic and the electronic contribution.     

Paramagnetic hyperfine structure of193Ir in K2IrCl6 diluted into K2PtCl6

The paramagnetic hyperfine splitting of Ir⁴⁺ (5d⁵) in K₂IrCl₆ diluted into diamagnetic K₂PtCl₆ has been observed at 4.2 K and Ir∶Pt ratios of 1∶10 and 1∶25. In the latter case a narrow paramagnetic pattern with a hyperfine coupling constant ofA=−13.1(2) mm/s was observed, but both samples also exhibit a single Ir⁴⁺ line typical for fast relaxation, either because of macroscopic inhomogeneities in the Ir distribution or because part of the Ir spins are still coupled to nearest Ir neighbours.     

Magnetfelder am Kern Ir193 in Verbindungen von Iridium mit Seltenen Erden

The hyperfine splitting and isomer shift of the 73 keV γ transition in Ir¹⁹³ was measured in the intermetallic compounds SmIr₂, GdIr₂, TbIr₂, DyIr₂, HoIr₂, and ErIr₂ using the Mössbauer effect. The electric field gradients, the electron densities, and the magnetic fields at the Ir nuclei were deduced from these experiments. An extensive discussion of the internal magnetic fields is given in terms of an empirical model.     

The hyperfine interaction of gadolinium and holmium in cubic Ho: (Gd,Ce)Fe2 compounds

The low-temperature hyperfine parameters of the ferrimagnetic C15 intermetallic system Ho_0.03Ce_xGd_0.97-xFe₂ have been measured at Gd using the 87 keV γ-ray of ¹⁵⁵Gd and at Ho using spin echo nmr of ¹⁶⁵Ho. A linear decrease of the hyperfine field B_t with increasing x is observed, the slope being almost the same for both nuclei. The observed slope (dB_t/dx ? -37T) is nearly three times greater than that found for ¹⁵⁵Gd in the analogous H₀:(Y, Gd)Fe₂ system; this is attributed to the influence of the increased conduction electron density when trivalent lanthanide ions are replaced by Ce⁴⁺.     

The hyperfine fields in ferromagnetic rare-earth zinc compounds with CsCl structure

A detailed analysis of the hyperfine interactions in a series of binary and pseudobinary ferromagnetic rare-earth zinc compounds (REZn; RE_{1 –x} A _x Zn; Gd_{1 –x} RE _x Zn; A: La, Y, Sc) is reported. With the help of the NMR spin echo technique the distance dependence of the hyperfine interaction is determined, without using a special model. The easy directions of magnetization of the pseudobinary compounds are deduced as well as the isotropic and anisotropic nearest neighbour hyperfine interaction. The data derived are discussed in terms of the electronic structure and the magnetic order in these compounds.D 17, Darmstädter Dissertation 1975.     

Structural, thermal and conductive properties of Bi4−xMxV2O11 (M = La, Gd; 0 x 0.4) compounds

Bi_4−xM_xV₂O₁₁ (M = La, Gd) was prepared by solid state reactions. The amount of La and Gd in the (Bi_4−xM_xV₂O₁₁) was varied in the range of (0 x 0.4). The addition of La and Gd to Bi₄V₂O₁₁ electrolyte was found to stabilize the β crystalline phase for x 0.3. In addition, the phase transition corresponding β- to γ-phases are evident in the ionic conductivity plots as well as in XRD, DSC profiles of x 0.3 samples. The highest ionic conductivity was observed in Bi_3.9La_0.1V₂O₁₁ and Bi_3.8Gd_0.2V₂O₁₁ samples in the range of 10⁻³–10⁻⁴ S/cm for 700–500 °C. These results were supported by impedance spectroscopy, X-ray diffraction (XRD) and differential scanning calorimetry (DSC).     

A novel Dy3+-doped Gd(PO3)3 white-light phosphors under VUV excitation for Hg-free lamps application

Novel Dy³⁺-doped Gd(PO₃)₃ white light phosphors each with an orthorhombic system are successfully synthesized by solid-state reaction. The luminescence properties of white-light Gd_1-x(PO₃)₃:xDy³⁺ (0<x≤ 0.25) under vacuum ultraviolet (VUV) excitation are investigated. The strong absorption at around 147 nm in excitation spectrum energy can be transferred to the energy levels of Dy³⁺ ion from the host absorption. Additionally, the white light phosphor is activated by a single Dy³⁺ ion. Therefore, the luminescence of Gd_1-x(PO₃)₃:xDy (0<x≤ 0.25) under VUV excitation is effective, and it has the promise of being applied to mercury-free lamp.     

Nuclear magnetic resonance on oriented192Ir in Fe and Ni

The hyperfine interaction of¹⁹²Ir nuclei as dilute impurities in Fe and Ni has been investigated with NMR on oriented nuclei. With the use of highly dilute and pure alloys the line widths could be reduced so far that the quadrupole splitting of¹⁹²IrFe and¹⁹²IrNi could be resolved. Taking hyperfine anomalies into account the ground state nuclear moments of¹⁹²Ir are deduced as |μ|=1.924(10)μ _N andQ=2.36(ll) b. The hyperfine field of IrNi was investigated as a function of the Ir concentrationc between 0.01 at % and 5 at %. The dependence ofH _HF onc was found to be significantly smaller than that reported from Mössbauer effect measurements. Forc=0.01 at %H _HF=?454.7(2.3)kG is deduced. The resonance shift with an external magnetic field has been studied precisely, yieldingK=0.012(23) andK=0.026(12) for the Knight-shift of¹⁹²Ir in Fe and Ni, respectively.     

The influence of hydrogen on55Mn hyperfine fields in YMn2 hydrides

The NMR spin ccho measurements at 4.2 K for YMn₂H_x (x=1, 2, 3) compounds are reported. The obtained values of⁵⁵Mn hyperfine fields are analysed in dependence on the by hydrogen atoms and flips of neighbouring manganese moments. The strong increase of hyperfine field with increasing number of the nearest hydrogen atoms is explained by the change of orbital contribution to hyperfine field.     

Magnetocaloric effect of compounds in Gd<Subscript>5−<Emphasis Type="Italic">x</Emphasis></Subscript>Dy<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>2</Subscript>Ge<Subscript>2</Subscript> system

Magnetization of magnetically ordered Gd_5−x Dy _x Si₂Ge₂ compounds with a partial substitution of Gd atoms by isovalent Dy atoms has been investigated. From temperature and field dependences of Gd_5−x Dy _x Si₂Ge₂ alloys with x = 0−2.0 changes of the magnetic part of entropy (ΔS _M ) of alloys are determined. It is established that ΔS _M achieves its maximum values at different temperatures, which linearly depend on the Dy concentration, and their values are comparable with ΔS _M ^max in Gd₅Si₂Ge₂. The obtained data allow us to conclude that the above-mentioned compounds have high magnetocaloric effect and are promising materials for using as a combined working body of magnetic refrigerators operating in the 200–270 K range of temperatures.     

155Gd Mössbauer spectroscopy measurements on Gd2T17C x,with T=Fe,Co, Ni andx varying from 0.6 to 1.2

¹⁵⁵Gd Mössbauer measurements were performed on Gd₂T₁₇C _x with T=Fe, Co, and Ni andx varying from 0.6 to 1.2. The crystal structures of these compounds are either the Th₂Zn₁₇ or the Th₂Ni₁₇ structure type. There is only partial occupation of the site available to the carbon atoms, leading to several crystallographically non-equivalent gadolinium surroundings. These various Gd sites show different quadrupole interactions. Doping with carbon causes an increased Curie temperature for the Gd₂Fe₁₇C _x compounds. The randomness of the occupation by carbon has been studied.     

X-ray magnetic circular dichroism at IrL2,3 edges in Fe100−x Ir x and Co100−x Ir x alloys: Magnetism of 5d electronic states

The formation of induced 5d magnetic moment on Ir in Fe_100−x Ir _x (x=3, 10 and 17) and Co_100−x Ir _x (x=5, 17, 25 and 32) alloys has been investigated by X-ray magnetic circular dichroism (XMCD) at Ir L_2,3 absorption edges. Sum rule analysis of the XMCD data show that the orbital moment of Ir is in the range of −0.071(2)μB to −0.030(1)μB in Fe-Ir alloys and −0.067(2)μB to 0.024(1)μB in Co-Ir alloys. We find that the total moment of Ir in Fe-Ir alloys is approximately 1/5 of the total 3d moment on Fe at all the three compositions. In contrast, the total moment on Ir in Co-Ir alloys varies between 1/6 to 1/16 of the 3d moment on cobalt. The observed trends of Ir moments and the role of interatomic exchange interactions in 5d moment formation are discussed.     

Magnetic properties of GdMg2 as studied by means of NMR and Mössbauer effect spectroscopy

The magnetic properties of GdMg₂ and Gd_xLa1-xMg2 were studied by means of magnetic measurements and spin echo NMR. The compounds GdMg₂, GdMg₃ and Gd₅Mg₂₄ were investigated by means of ¹⁵⁵Gd Mössbauer spectroscopy. The results of the various measurements indicate the presence of a relatively strong 5d electron density of states.