59Co nuclear magnetic resonance study in GdCo2Si2 compound

The spin echo NMR spectra of⁵⁹Co for GdCo₂Si₂ are reported. A weak negative hyperfine field on Co nuclei was found in magnetically ordered state of the compound. The splitting of resonance lines in external magnetic field indicates on antiferromagnetic structure of Gd moments lying in thea-a plane with energetic minima in [100] and [110] directions as in GdFe₂Si₂ and GdNi₂Si₂.     

Transient and pulsed EPR study of17O-substituted methyl-naphthoquinone as radical anion in the A1 binding site of photosystem I and in frozen solution

Quinones have been studied in considerable detail as functional cofactors in membrane-bound protein-cofactor systems, in particular in reaction centers (RCs) of photosynthesis. For both types of RCs, they act primarily as one-electron gates during light-induced charge separation but at very different redox potential. Hydrogen bonding between the RC protein and the two, 1,4-quinone carbonyl groups constitutes a major protein-cofactor interaction in control of function. In contrast to symmetric H-bonding for quinones in isotropic solution, asymmetric H-bonding is a characteristic feature of the quinone binding sites in RC proteins. A simple valence bond model correlates the asymmetry of respective H-bond strength with the asymmetric spin density distribution derived from observable hyperfine couplings of the quinone anion state. Among all quinone-protein systems studied so far, the A₁ acceptor site in photosystem (PS) I exhibits the highest asymmetry. Since the carbonyl groups carry most of the total unpaired electron spin density, isotopic labelling of the carbon (¹³C) and oxygen (¹⁷O) appears to be the proper way to characterize the H-bond asymmetry by hyperfine couplings. Indeed, recent¹³C hyperfine studies, together with data for protons in specific ring substituents, confirm the high asymmetry correlated with only one dominant H-bond in the A₁ site of PS I, which is consistent with the structure model derived from X-ray structure (1JB0) for the ground state of the PS I protein complex.¹⁷O hyperfine tensors measured for the A₁ site of PS I yield high hyperfine coupling constants but very small asymmetry for the two carbonyl groups. The asymmetry is even three times smaller than the already small one observed for the Q_A site of purple bacterial RCs. A small asymmetry is however consistent with previous studies on model systems which showed an insensitivity of the¹⁷O hyperfine coupling to H-bond-induced changes of the unpaired electron spin density. The large¹⁷O hyperfine coupling itself appears to depend on the electrostatics seen by the radical anion. It is slightly larger when A ₁ ^? is part of the functional transient radical ion pair state as compared with the photoaccumulated stable radical anion. Possible explanations and consequences of these results are discussed.     

Magnetic behaviour of NpAs2 from Mössbauer spectroscopy

The Mössbauer hyperfine spectra of the 60 keV resonance of ²³⁷Np in powder and single crystal absorbers of NpAs₂ were measured between 4.2 and 60 K. Below 18 K a simple magnetic plus quadrupole pattern is seen in accordance with a ferromagnetic spin structure in tetragonal NpAs₂. The isomer shift favors the 4+ charge state, the hyperfine field of 288 T implies a moment of 1.5μ_B at the Np ion. The large reduction compared to the free ion values points towards a strong mixing of the electronic ground state by crystalline field interactions. Above 18 K the spectrum changes into a complex hyperfine pattern indicating a sinusoidally modulated spin structure. Near 54 K a transition into the paramagnetic state is observed. Both magnetic transitions (18 and 54 K) exhibit a feature typical for a first-order character.     

Pulsed ESR investigations of anisotropic interactions in M@C82 (M=Sc,Y,La)

82 , Y@C₈₂, and La@C₈₂ in frozen solutions. We were able to determine the g tensors of these molecules by analysing magnetic field spectra at X-band (9.5 GHz) and W-band (94 GHz) frequencies. Moreover, in Y@C₈₂ we have investigated the hyperfine interaction of the ⁸⁹Y nuclear spin (I=1/2) with the electron spin on the C₈₂ cage. The principal values of the hyperfine tensor A and the relative orientation of g and A tensors were determined by applying three- and four-pulse electron spin echo envelope modulation techniques (ESEEM). Received: 3 September 1997/Accepted: 10 November 1997     

Transferred hyperfine field in the pseudo-binary compound Y(Fe,Mn)2

The NMR of⁸⁹Y in Y(Fe_1−xMn_x)₂ has been observed. Two kinds of Mn moments were estimated by analyzing the⁸⁹Y hyperfine field: (1) the low spin state with about 0.6 μ_B in antiparallel to Fe moment and (2) the high spin state with about 2.8 μ_B in parallel to Fe moment. The magnetizations estimated from NMR results are in good agreement with those of magnetization measurements.     

Anomalous hyperfine field and orbital moment of cobalt in RCo2; R = Pr,Nd, Sm,Gd, Tb,Dy, Ho,Er and Tm

⁵⁹Co spin echo NMR spectra in the magnetically ordered phase of the MgCu₂ type RCo₂ compounds (R = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er and Tm) have been observed. For the RCo₂ with the easy direction of magnetication parallel to the 〈011〉 or 〈111〉 direction, the ⁵⁹Co hyperfine fields at two magnetically inequivalent Co sites are found to be antiparallel, revealing a large anisotropy in the ⁵⁹Co hyperfine field. The results are discussed in terms of a large and anisotropic orbital moment of Co. The transferred hyperfine field due to rare earth spins is estimated from well resolved satellite lines observed in Tb_1?xY_xCo₂. The nuclear quadrupole splitting in the magnetically ordered phase is found to be always larger than that in the paramagnetic phase.     

<Superscript>53</Superscript>Cr NMR study of CuCrO<Subscript>2</Subscript> multiferroic

The magnetically ordered phase of the CuCrO₂ single crystal has been studied by the nuclear magnetic resonance (NMR) method on ⁵³Cr nuclei in the absence of an external magnetic field. The ⁵³Cr NMR spectrum is observed in the frequency range ν_res = 61–66 MHz. The shape of the spectrum depends on the delay tdel between pulses in the pulse sequence τ_π/2–t _del–τ_π–t _del–echo. The spin–spin and spin–lattice relaxation times have been measured. Components of the electric field gradient, hyperfine fields, and the magnetic moment on chromium atoms have been estimated.     

NMR study of some heusler alloys containing Co and Mn

The⁵⁹Co and⁵⁵Mn NMR were measured at 4.2 K by spin echo technique. The hyperfine fields in Co₂ MnAl and Co₂MnSb were determined, and it was suggested that in the Co₂MnZ compounds the Co hyperfine field depends on Z. The magnitude of the hyperfine field at Mn dilutely dissolved in Co₂TZ by replacing T (T=Ti, V, Cr, Fe) was found to be larger by 30–80 kOe than that in Co₂MnZ with the same Z. The hyperfine field at Co dilutely dissolved in X₂ MnZ (X=Ni, Cu) by replacing X had a value quite near to that in Co₂MnZ.     

EPR Study of Sc<Subscript>2</Subscript>SiO<Subscript>5</Subscript>:Nd<Superscript>143</Superscript> Isotopically Pure Impurity Crystals

The Sc₂SiO₅ single crystals doped with 0.001 at.% of the ¹⁴³Nd³⁺ ion were studied by continuous-wave and pulse electron paramagnetic resonance methods. The g-tensors and hyperfine structure tensors for two magnetically non-equivalent Nd ions were obtained. The spin–spin and spin–lattice relaxation times were measured at 9.82 GHz in the temperature range from 4 to 10 K. It was established that three relaxation processes contribute to the spin–lattice relaxation processes. There are one-phonon spin–phonon interaction, two-phonon Raman interaction and two-phonon Orbach–Aminov relaxation processes. It was established that spin–spin relaxation time is of the same magnitude for neodymium ion doped in Sc₂SiO₅ and in Y₂SiO₅.     

Magnetic phase transitions and iron valence in the double perovskite Sr 2 FeOsO 6

The insulating and antiferromagnetic double perovskite Sr₂FeOsO₆ has been studied by ⁵⁷Fe Mössbauer spectroscopy between 5 and 295 K. The iron atoms are essentially in the Fe^3?+? high spin $( {t_{2\mathrm{g}}{^3} e_\mathrm{g}{^2} } )$ and thus the osmium atoms in the Os $^{5+} ( {t_{2\mathrm{g}}{^3} } )$ state. Two magnetic phase transitions, which according to neutron diffraction studies occur below T _N?= 140 K and T ₂?= 67 K, give rise to magnetic hyperfine patterns, which differ considerably in the hyperfine fields and thus, in the corresponding ordered magnetic moments. The evolution of hyperfine field distributions, average values of the hyperfine fields, and magnetic moments with temperature suggests that the magnetic state formed below T _N is strongly frustrated. The frustration is released by a magneto-structural transition which below T ₂ leads to a different spin sequence along the c-direction of the tetragonal crystal structure.     

Mössbauer spectroscopy of the new iron oxide Fe3B7O13(OH)

In order to investigate the electronic state, the local structure, and the magnetic structure of a new ion oxide Fe₃B₇O₁₃(OH), we have applied ⁵⁷Fe Mössbauer spectroscopy. The room-temperature values of isomer shift and quadrupole splitting are 1.16 mm/s and 3.21 mm/s, respectively, which indicate that the Fe ions are in high spin Fe^2?+? state. The spectrum at 4.2 K is composed of a well-resolved hyperfine sextet with the hyperfine field of 3.6 T. In a trimer, each Fe^2?+? magnetic moment is supposed to be directed from Fe^2?+? to OH^???.     

EPR of Er3+, Nd3+, and Ce3+ ions in YAlO3 single crystals

EPR spectra of the Er³⁺, Nd³⁺, and Ce³⁺ ions substituting for the Y³⁺ ion in the YAlO₃ yttrium orthoaluminate lattice are studied. The EPR spectra of these rare-earth ions are described by a spin Hamiltonian of rhombic symmetry with an effective spin S=1/2. The principal values of the g tensors were determined from an analysis of the angular dependences of the EPR spectra. The orientation of the local magnetic axes of paramagnetic centers relative to the YAlO₃ crystallographic directions are shown to depend on the actual rare-earth species. The EPR spectra exhibit a hyperfine structure due to the ¹⁶⁷Er, ¹⁴³Nd, and ¹⁴⁵Nd odd isotopes, which permitted unambiguous identification of these spectra. The hyperfine coupling constants for the odd erbium and neodymium isotopes are determined.     

The lowest triplet state of luminescent scheelites: a study of the MoO24- ion by electron paramagnetic resonance with optical detection

The fine-structure and g tensors of the luminescent triplet state of the molybdate anion in single-crystals of CaWO₄:MoO₄, CdMoO₄ and PbMoO₄, all with the scheelite structure, are reported. In all three hosts the MoO24- ion is distorted on excitation. The directions of the principal axes of the fine-structure and g tensors support the idea that the effect results from the combined action of a Jahn-Teller instability and the crystal field. The hyperfine coupling of the ⁹⁵Mo and ⁹⁷Mo nuclei points towards excitation to an orbital with a large contribution of Mo 4d_3z2-2r.     

Magnetic hyperfine interactions and compositional short range order in the Heusler alloys Cu2MnIn1-xSnx

A comprehensive study of the magnetic hyperfine interactions and the processes of crystallographic ordering in the Heusler alloy system Cu₂MnIn_1-xSn_x has been made. We report the results of Mössbauer effect experiments, X-ray diffraction studies, electrical transport, and Curie temperature measurements. By a rapid quenching, low temperature annealing technique we have been able to extend the ordered L2₁ structure to high Sn concentration. Observations of inequivalent Sn sites and nonunique ¹¹⁹Sn hyperfine field values in these alloys are shown to be due to difficulties in ordering the L2₁ structure and a basic instability of this phase for high Sn concentrations. The compositional variation of ¹¹⁹Sn hyperfine fields in the ordered L2₁ phase of the Cu₂MnIn_1-xSn_x system reveals a systematic increase with Sn composition. Calculations of these fields based on a homogeneously spin polarized electron gas model reproduce the observed field systematics quite well. The implications of these results on the nature of magnetic interactions in Heusler alloys are discussed.     

Local magnetic structure and anomalies of magnetic hyperfine interactions of57Fe and119Sn nuclei in lithium aluminium ferrites

The⁵⁷Fe and¹¹⁹Sn Mossbauer spectra of ordered ferrites Li_0.5Fe_2.5−xAl_xO₄∶Sn for 0.8<x<1.0 (the compensation point region) have been studied. The spin glass type magnetic structure with the spin canting angle depending on temperature and aluminium concentration is established. Anomalies in the temperature dependence of the hyperfine magnetic field at tin nuclei have been found near the compensation point of the ferrites     

Spin dynamics in LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> low-dimensional helical magnets

Comprehensive NMR investigation of low-frequency spin dynamics of LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) low-dimensional helical magnets in the paramagnetic state has been carried out for the first time. Temperature dependences of the spin–lattice relaxation rate and anisotropy on various LCO/NCO nuclei have been determined at various orientations of single crystals in an external magnetic field. The spatial asymmetry of spin fluctuations in LCO multiferroic has been discovered. The quantitative analysis of the anisotropy of spin–lattice relaxation in LCO/NCO has allowed estimating the contributions of individual neighboring Cu²⁺ ions to the transferred hyperfine field on Li⁺(Na⁺) ions.     

E.S.R. spectra of SiF3 radicals produced in a single crystal of SiF4

E.S.R. spectra of a γ-irradiated single crystal of SiF₄ were investigated. The spectra observed were attributed to SiF₃ radicals having ²⁸Si (I=0) and ²⁹Si (I=1/2) atoms. From the angular dependence of the spectral lines on rotation of the single crystal, hyperfine tensors were determined for three fluorine atoms and the ²⁹Si atom of the SiF₃ radical. The three fluorine atoms in the radical are equivalent, whereas the directions of their hyperfine tensors are different from one another owing to the pyramidal structure of the radical. In addition to the hyperfine analysis, the analysis of the superhyperfine structure due to neighbouring fluorine atoms gave information on the orientation of the radicals in the crystal and the mechanism of radical formation. The structure of the radical is discussed in comparison with that of the CF₃ radical.     

NMR study of the paramagnetic state of low-dimensional magnets LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript> and NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript>

A comprehensive NMR study of the magnetic properties of single crystal LiCu₂O₂ (LCO) and NaCu₂O₂ (NCO) is carried out in the paramagnetic region of the compounds for various orientations of single crystals in an external magnetic field. The values of the electric-field gradient (EFG) tensor, as well as the dipole and transferred hyperfine magnetic fields for ^63,65Cu, ⁷Li, and ²³Na nuclei are determined. The results are compared with the data obtained in previous NMR studies of the magnetically ordered state of LCO/NCO cuprates.     

Structural,magnetic and151Eu Mössbauer studies on EuTCu4 (T-Al,Pd and Ag) compounds

New ternary compounds having the formula EuTCu₄ where T=Al, Pd and Ag have been synthesized. All these compounds are found to crystallize in the hexagonal CaCu₅ type structure. Magnetization measurements reveal that these compounds are magnetically ordered with magnetic moments close to 7 μ_B. The Curie temperatures obtained from low field ac susceptibility measurements are 26K, 25K and 50K for T-Al, Pd and Ag respectively.¹⁵¹Eu Mössbauer studies at room temperature show a large negative isomer shift relative to SmF₃. A hyperfine split pattern is observed at 4.2K in all these compounds, indicating that Eu ion is present in a divalent state and is magnetically ordered.     

Theoretical spin density in nitroxides

The evolution of the hyperfine tensors in the nitroxide series with increasing alkyl substitution on the NO group has been studied theoretically for radicals from H₂NO to C₅H₁₀NO. A projection technique has been applied to the UHF wave-functions in order to correct spin densities for quartet contamination. The magnitude of the isotropic and anisotropic couplings reflects the substitution effect already observed on the spin distribution maps, that is a spin transfer from oxygen to nitrogen when alkyl groups are substituted to hydrogens in H₂NO. The alternation of the signs of the couplings along the chain as well as the cos² γ law for the coupling constants of atoms (C or H) in β position are verified in the series. The orientation of the anisotropic tensors with respect to the chemical bonds depends on the position of the atoms in the molecule (radical site, α, β positions); it is not affected by further substitution, except for strongly asymmetric configurations.