Precise nuclear moments of extremely proton-rich nuclus 23 Al

Electric quadrupole coupling constant eqQ/h of the extremely proton-rich ²³Al (I ^π ?=?5/2^?+?, T _1/2?=?0.47 s) nucleus implanted into an Al₂O₃ single crystal has been measured for the first time, using the β-ray detecting nuclear quadrupole resonance method (β-NQR) in a high magnetic field. As a preliminary result, the quadrupole coupling constant was determined as |eqQ/h(²³Al) |?=?2.66±0.77 MHz. Using the quadrupole coupling constant of ²⁷Al in Al₂O₃ as a reference, the Q moment of the ground state of ²³Al was extracted as |Q(²³Al)|?~?160 mb, which is well explained by the shell model calculation in the sd-shell model space with the USD interaction.     

Synthesis and characterisation of the Fe(II–III) hydroxy-formate green rust

A new methodology was envisioned in order to prepare green rust compounds build on organic anions that could intervene in microbiologically influenced corrosion processes of iron and steel. The formate ion was chosen as an example. The formation of rust was simulated by the oxidation of aqueous suspensions of Fe(OH)₂ precipitated from Fe(II) lactate and sodium hydroxide, in the presence of sodium formate to promote the formation of the corresponding green rust. The evolution of the precipitate with time was followed by transmission Mössbauer spectroscopy at 15 K. It was observed that the initial hydroxide was transformed into a new GR compound. Its spectrum is composed of three quadrupole doublets, D ₁ (δ?=?1.28 mm s^?1, Δ?=?2.75 mm s^?1) and D ₂ (δ?=?1.28 mm s^?1, Δ?=?2.48 mm s^?1) that correspond to Fe(II) and D ₃ (δ?=?0.49 mm s^?1, Δ?=?0.37 mm s^?1) that corresponds to Fe(III). The relative area of D ₃, close to the proportion of Fe(III) in the GR, was found at 28.5?±?1.5% (～2/7). Raman spectroscopy confirmed that the intermediate compound was a Fe(II–III) hydroxy-formate, GR(HCOO^?).     

Local and dynamic Jahn-Teller distortion in ulvöspinel Fe2TiO4

⁵⁷Fe Mössbauer spectroscopic study on ulvöspinel Fe₂TiO₄ has been conducted in a wide temperature range from 16 K to 500 K. The paramagnetic spectra are composed of several high spin Fe^2?+? doublets even at 500 K, which is rather strange because the point symmetry of the A-site is completely cubic (??43m). We explain the electric field gradient (EFG) at A-site by the local arrangement of Fe^2?+? and Ti^4?+? on the B-site. The spectra were successfully analyzed by four-subspectra model, which is based on the B-site arrangement. The model also fits rather well to the magnetically ordered spectra. Thus the temperature variations of the hyperfine parameters were obtained. The Néel temperature (T _N) is estimated to be about 125 K. The quadrupole coupling constants e ² qQ/2 of A-site subspectra show little change around cubic-tetragonal transition temperature (T _t?=?163 K), but rapidly increase below T _N. From the temperature variation of line width, we found local and dynamic Jahn-Teller distortions around A-site Fe^2?+? ions in the cubic phase.     

Hyperfine interactions in intermetallic rare earth-gallium compounds studied by 111 Cd PAC

Magnetic and electric hyperfine interaction of the nuclear probe ¹¹¹In/¹¹¹Cd in intermetallic compounds of the rare earth-gallium system have been investigated by perturbed angular correlation (PAC) spectroscopy. The PAC measurements, supported by X-ray diffraction, provide evidence for a marked phase preference of ¹¹¹In for hexagonal RGa₂ over orthorhombic RGa and of RGa₃ with the L12 structure over RGa₂. In the case of SmGa₂, the magnetic hyperfine field B_hf, the electric quadrupole interaction and the angle β between B_hf and the symmetry axis of the electric field gradient have been determined as a function of temperature. The angle β?=?0 is consistent with the results of previous magnetization studies. Up to T?≤?17 K the magnetic hyperfine field has a constant value of B_hf?=?3.0(2) T. The rapid decrease at higher T gives the impression of a first-order transition with an order temperature of T_N?=?19.5 K. In the RKKY model of indirect 4f interaction the ratio T_C/B_hf(0) is a measure of the coupling constant. For ¹¹¹Cd:SmGa₂ (T_C/B_hf(0)~6.5 K/T) this ratio is significantly smaller than for the same probe in other R intermetallics (SmAl₂ ~9.5 K/T, Sm₂In ~13.5 K/T).     

A new one-dimensional hybrid material lattice: AC conductivity and structural characterization of [C<Subscript>7</Subscript>H<Subscript>12</Subscript>N<Subscript>2</Subscript>][CdCl<Subscript>4</Subscript>]

The present paper reports the synthesis, crystal structure, ¹³C and ¹¹¹Cd cross-polarization magic-angle spinning nuclear magnetic resonance(CP-MAS-NMR) analysis and ac conductivity for a new organic–inorganic hybrid salt, [C₇H₁₂N₂][CdCl₄]. The compound crystallizes in the triclinic system, space group P\( \overline 1 \), with unit cell dimensions: a?=?7.1050(3) Å, b?=?8.9579(3) Å, c?=?9.4482(3) Å, α?=?81.415(1)°, β?=?89.710(2)°, γ?=?85.765(1)°, V?=?592.97(4) Å³, and Z?=?2. The asymmetric unit is composed of one-2,4-diammonium toluene cation and one [CdCl₄]^2? anion. The Cd atom is in a slightly distorted octahedra coordination environment. Its structure can be described by infinite chains of CdCl₆ octahedron linked to organic cations by a strong charge-assisted N–H???Cl interactions in order to build organic–inorganic layers staked along \( \left[ {0\overline 1 1} \right] \) direction. The solid state ¹³C CP-MAS-NMR spectra has shown seven isotropic resonances, confirming the existence of seven non-equivalent carbon atoms, which is consistent with crystal structure determined by X-ray diffraction. As for ¹¹¹Cd MAS-NMR, it has shown one cadmium site with isotropic chemical shift observed at 167.2 ppm. The complex impedance of the compound has been investigated in the temperature range of 403–460 K and in the frequency range of 200 Hz–5 MHz. The impedance plots have shown semicircle arcs at different temperatures and an electrical equivalent circuit has been proposed to explain the impedance results. The circuits consist of the parallel combination of bulk resistance R _p and constant phase elements.     

57Fe Mössbauer study of new multiferroic AgFeO2

The present work reports results of the ⁵⁷Fe Mössbauer measurements on AgFeO₂ powder sample recorded at various temperatures including the points of both magnetic phase transitions. The ⁵⁷Fe Mössbauer spectra of AgFeO₂ measured in the paramagnetic range (T > T _N1) consist of one quadrupole doublet with rather high quadrupole splitting of Δ_300K = 0.66 ± 0.01 mm/s for Fe³⁺ ions. In order to predict the sign of electric field gradient (EFG) at ⁵⁷Fe nuclei, we calculated the lattice contribution to the electric field gradient (EFG) at ⁵⁷Fe nuclei, which emphasized the importance of the dipolar contributions, with resultant oxygen polarizabilities in the range of α _O = 0.83 ų, in agreement with the results obtained previously for other delafossite-like oxides. In the temperature range of T _N2 < T < T _N1, Mössbauer spectra gave clear evidence for the existence of a distribution of the hyperfine magnetic fields H _hf at ⁵⁷Fe nuclei. We present the results of a model fitting of the spectra based on an assumption of the cycloid magnetic structure of AgFeO₂ at T < T _N2. The obtained data were analysed in comparison with published data on Mössbauer studies of oxide multiferroics.     

Electric quadrupole moments of neutron-rich nuclei 32Al and 31Al

The electric quadrupole moments for the ground states of ³²Al and ³¹Al have been measured by the β ray-detected nuclear quadrupole resonance method. Spin-polarized ³²Al and ³¹Al nuclei were obtained from the fragmentation of ⁴⁰Ar projectiles at E/A?=?95 MeV/nucleon, and were implanted in a single crystal α-Al₂O₃ stopper. The measured Q moment of ³²Al, |Q(³²Al)|?=?24(2) mb, is in good agreement with a conventional shell-model calculation with a full sd model space and empirical effective charges, while that of ³¹Al is considerably smaller than the sd calculations.     

Spin-lattice relaxation of 25Al and 28P in Pt

The spin-lattice relaxation times T ₁ for short-lived β emitters ²⁵Al(I?=?5/2, T _1/2?= 7.2 s) and ²⁸P(I?=?3, T _1/2?= 270 ms) in Pt were measured by means of the β-NMR technique. As a result, T ₁[²⁵Al in Pt] = (1.1 $^{+\ 0.7}_{-\ 0.3})$ s and T ₁[²⁸P in Pt] >0.5 s were obtained at temperatures of 17 and 20 K, respectively. The Knight shifts were estimated from the Korringa relation, which were evaluated by comparing to the first principle calculations.     

Synthesis,crystal structure,thermal analysis,and electrical properties of bis tetrapropylammonium hexachloro-dizincate compound

The present paper accounts for the synthesis, crystal structure, differential scanning calorimetry, vibrational study, and electrical properties of the [N(C₃H₇)₄]₂Zn₂Cl₆ compound. The latter is crystallized at room temperature in the triclinic system ( $ P\overline{1} $ space group) with the following unit cell parameters: a?=?13.736(2)Å, b?=?17.044(3)Å, c?=?17.334(2)Å, α?=?68.30(2)°, β?=?75.14(2)°, and γ?=?84.93(3). The atomic arrangement can be described by alternating organic and inorganic layers parallel to the (001) plan, made up of [N(C₃H₇)₄]⁺ groups and [Zn₂Cl₆]^2? dimers, respectively. In crystal structure, the inorganic layer, built up by Zn₂Cl₆ dimers, is connected to the organic ones through van der Waals interaction in order to build cation–anion–cation cohesion. The infrared and Raman studies confirm the presence of the organic group tetrapropylammonium and the Zn₂Cl₆ anion. Concerning the differential scanning calorimetry, it revealed two reversible solid–solid phase transitions of first order: at 327/324 K and 347/343 K (heating/cooling). Besides, the impedance spectroscopy study, reported in the sample, reveals that the conduction in the material is due to a hopping process. Regarding the temperature dependence of the dc conductivity, it suggests Arrhenius type: σ _dc T?=?B ?exp(?E _a /kT). The tetrapropylammonium cations appeared to be the most sensitive to the phase transition.     

A Novel Ratiometric Fluorescent Mercury Probe Based on Deprotonation-ICT Mechanism

A new NBD-rhodamine dye (1) was developed as a colorimetric and ratiometric fluorescent chemosensor for Hg²⁺ with good selectivity in aqueous ethanol solutions under neutral to basic conditions. Sensor 1 showed absorption at 468 nm and a weak emission at 529 nm (? _F ?=?0.063) in ethanol/aqueous tris buffer (9:1, v/v) of pH 9.17 solution. Bathochromic shifts in both absorption (492 nm) and fluorescence spectra (569 nm, ? _F ?=?0.129), respectively upon addition of 2 equiv. of Hg²⁺ were observed. The ring-opening reaction of the spirolactam form to the corresponding xanthene form was not found. The interaction of Hg²⁺ with chemosensor 1 resulted in the deprotonation of the secondary amine conjugated to the NBD component so that the electron-donating ability of the N atom was enhanced. Deprotonation-ICT mechanism of secondary amines was suggested for the ratiometric fluorescent chemosensing for Hg²⁺.     

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.     

Static electric quadrupole interaction of Ta- and Hf-ions in barium and lead titanate

The static electric quadrupole interaction of¹⁸¹Ta and¹⁷⁸Hf in polycrystalline barium and lead titanate at the site of titanium has been measured using time differential PAC and the Mössbauer effect. The electric field gradients (EFG) at room temperature at the¹⁸¹Ta nucleus are ¦V _zz¦=(3.6±0.2)·10¹⁷V/cm² in BaTiO₃ and ¦V _zz¦=(14.6±0.6)·10¹⁷ V/cm² in PbTiO₃. The temperature dependence of the quadrupole interaction has been studied giving the following EFG values: ¦V _zz¦=(2.4±0.2)·10¹⁷ V/cm² in the monoclinic and ¦V _zz¦=(1.1±0.3)·10¹⁷ V/cm² in the rhomboedral phase of BaTiO₃, and ¦V _zz¦=(15.7±0.6)·10¹⁷ V/cm² for¹⁸¹Ta/PbTiO ₃ at 77 °K. The EFG of¹⁷⁸Hf in PbTiO₃ has been derived from a Mössbauer effect experiment to beV _zz=+(10.7±0.5)·10¹⁷ V/cm². The results are compared with EFG's calculated in a point charge model and with experimental EFG's measured at⁴⁴Sc and⁵⁷Fe in the same titanates by other authors. Contributions of covalent bonds to the effective EFG's in perovskit crystals are discussed.     

57Fe Mössbauer spectroscopic study of (25−x)MnO–xZnO–15Fe2O3–60B2O3 glasses

The ⁵⁷Fe Mössbauer technique has been used to investigate the effect of zinc oxide substitution in (25???x)MnO–xZnO–15Fe₂O₃–60B₂O₃ glass system (x?=?0, 5, 10, 15 and 20 mol% of ZnO ). Mössbauer absorption spectra for all the samples recorded at room temperature suggest the existence of the two paramagnetic quadrupole doublets. The observed variations in hyperfine parameters have been explained on the basis of cations distribution and exchange interaction at the lattice sites and it is concluded that B–B interaction increases while the metal–metal interaction decreases due to replacement of manganese oxide by zinc oxide. These results suggest that the present glass system exhibits a paramagnetic behaviour that changes towards the weak paramagnetic when manganese oxide was replaced with zinc oxide.     

Phase transition and proton exchange in 1,3-diazinium hydrogen chloranilate monohydrate

In the hydrate crystal of 1:1 salt with 1,3-diazine and chloranilic acid (H₂ca), (1,3-diazineH)·H₂O·Hca, an unique hydrogen-bonded molecular aggregate is formed. There exists proton disorder in the N–H...O hydrogen bond between 1,3-diazinium ion and water (H₂O) of crystallization. In order to reveal dynamic aspect of this disorder, ³⁵Cl NQR measurements were conducted. Two resonance lines observed at 35.973 and 35.449 MHz at 321 K split into four lines below T _c?=?198 K clearly showing occurrence of a solid–solid phase transition; 36.565, 36.357, 36.011, 35.974 MHz at 77 K. Temperature dependence of spin-lattice relaxation time T ₁ in high-temperature phase was observed to obey an Arrhenius-type relation with the activation energy of 8.5 kJ mol^???1. This result leads to the conclusion that proton exchange in the N–H...O hydrogen bond takes place in the high-temperature phase. Specific heat measurements by DSC resulted in the transition entropy ΔS?=?1.3 J K^???1 per 1 mole [(1,3-diazineH)·H₂O·Hca]₂ which is far less than 2R ln2 = 11.5 J K^???1 mol^???1. It is expected that proton exchange in the two hydrogen bonds within the aggregate does not occur independently but concertedly with strong correlation in the high-temperature phase.     

X-ray structure refinement and ionic conductivity of Na6.69Ca3.355(SO4)6Cl0.77F0.63

The structure of Na_6.69Ca_3.355(SO₄)₆Cl_0.77F_0.63, isostructural with fluorapatite, was determined by X-ray powder diffraction methods. The results of Rietveld refinement revealed a space group P6₃/m with lattice parameters of a?=?9.477 (2) Å, c?=?6.865 (5) Å. Final refinement led to R _F?=?1.83 % and R _B?=?7.64 %. The location of Na⁺ ions in the M (2) sites surrounding the channels was related particularly to the high polarizability of the Ca²⁺. The ionic conductivity over a wide range of temperature was investigated according to the complex impedance method. The highest overall conductivity values were found at σ _500 °C?=?1.03?×?10^?5?S?cm^?1 and E_a?=?0.70 eV.     

Mössbauer and XRD study of pulse plated Fe–P and Fe–Ni thin layers

⁵⁷Fe conversion electron Mössbauer spectroscopy, X-ray diffraction, electrochemical and magnetic measurements were used to study pulse electroplated Fe–P and Ni–Fe coatings. XRD and ⁵⁷Fe CEMS measurements revealed the amorphous character of the novel pulse plated Fe–P alloys. CEM spectra indicated significant differences in the short range order and in the magnetic anisotropy between the Fe–P deposits pulse plated at medium long deposition time (t _on?=?2 ms), with short relaxation time (t _off?=?9 ms) and low current density (I _p?=?0.05 Acm^?2) or at short deposition time (t _on?=?1 ms) with long relaxation time (t _off?=?250 ms) and high current density (I _p?=?1.0 Acm^?2). The broad peaks centred around the fcc reflections in XRD of the pulse plated Ni-22 wt.% Fe deposit reflected a microcrystalline Ni–Fe alloy with a very fine, 5–8 nm, grain size. The CEM spectrum of the pulse plated Ni-22 wt.% Fe coating corresponded to a highly disordered solid solution alloy containing a minute amount of ferrihydrite. Extreme favourable soft magnetic properties were observed with these Ni–Fe and Fe–P pulse plated thin layers.     

Isotope ratio of Cl NQR spin-lattice relaxation times in 1D hydrogen-bonding system of tetramethylpyrazine-chloranilic acid at high temperatures

The temperature dependences of spin-lattice relaxation time T ₁ of ³⁵Cl and ³⁷Cl NQR were studied for the co-crystal of tetramethylpyrazine (TMP) with chloranilic acid (H₂ca), TMP-H₂ca, in which one-dimensional hydrogen bonding is formed by alternate arrangement of TMP and H₂ca. The isotope ratio ³⁷Cl T ₁ / ³⁵Cl T ₁ was determined to be 1.0 ± 0.1 above ca. 290 K where a steep decrease of spin-lattice relaxation time T ₁ with increasing temperature was observed. In this temperature range it is suggested that the relaxation is originated from the slow fluctuation of electric field gradient (EFG). Beside EFG fluctuation due to the external-charge-density fluctuation, the small angle reorientation of the quantization axis triggered by a proton transfer motion between N...H-O and N-H...O hydrogen bonding states is proposed.     

Production of 62Zn radioactive nuclear beam and on-line PAC investigation of quadrupole interaction in nano-magnetic material Fe73.5Cu1Nb3Si13.5B9

An Isotope Separator On-Line (ISOL), dedicated to on-line perturbed angular correlation (PAC) and positron annihilation spectroscopy (PAS), has been constructed at CIAE based on the HI-13 tandem accelerator, and a 30 keV radioactive beam of ⁶²Zn with intensity of 2 ×10⁷/s produced by it. Using the ⁶²Zn radioactive beam the investigation of the nano-crystalline soft magnetic Fe_73.5Cu₁Nb₃Si_13.5B₉ materials has been fulfiled for the first time by the on-line time differential PAC technique. Two quadrupole interaction frequencies ω ₀₁ (?=?440 Mrad/s) and ω ₀₂ (?=?90 Mrad/s) were gained, indicating there are two implantation sites of ⁶²Zn. The frequency ω ₀₂ shows a fluctuation of the crystal lattice constants and proves the characteristic distribution model of nano-crystalline grain boundary. The frequency ω ₀₁ demonstrates that the implanted ⁶²Zn occupies the site of the ordered grain core. The fractions of ω ₀₁ and ω ₀₂ are f₀₁?=?38 % and f₀₂?=?62 %, respectively.     

Search for magnetic interaction in In doped AlN using perturbed angular correlation spectroscopy

The possible presence of a large magnetic field due to spin polarization of a Cd nucleus (decay product of ¹¹¹In) at an Al substitutional site in AlN is investigated with perturbed angular correlation (PAC) spectroscopy. The PAC spectra of ¹¹¹In/¹¹¹Cd in AlN show two probe environments: a weak quadrupole interaction (quadrupole interaction constant, $\nu _{\rm Q}^{\,\,\,\rm lattice} = 30$  MHz) due to ¹¹¹In probes at a defect free Al substitutional site and an unknown large interaction ( $\nu _{\rm Q}^{\,\,\,\rm complex} = 300$  MHz) tentatively attributed to a nearest neighbour pair between ¹¹¹In and a nitrogen vacancy (V_N) aligned along the c-axis. Surprisingly, in density functional theory (DFT) calculations, such a large electric field gradient (EFG) could not be reproduced. However, an inclusion of spin polarization in the calculations indicates a strong magnetic field at ~50 % of the ¹¹¹In/¹¹¹Cd site. An attempt to verify the presence of the strong magnetic field and to explain the origin of the strong interaction is made. Orientation measurements show, the large interaction is not characterised by a magnetic interaction and is predominantly due to the EFG. However, in the presence of an external magnetic field, the strong interaction probe environment becomes more uniform and the EFG increases by ~10 %. This definitely hints towards some sort of magnetic interaction at the strong interaction probe site.     

Electric field gradients at 151Eu sites in GaN

The electric field gradients at Eu sites in GaN have been investigated in conversion electron Mössbauer spectroscopy (CEMS) in which ¹⁵¹Eu probe ions were implanted into an undoped GaN layer grown on a sapphire substrate. The sample was implanted with 120 keV ¹⁵¹Eu ions to a fluence of 1 × 10¹⁵, and annealed at 1,200 K. CEMS spectra of the ¹⁵¹Eu 21.6 keV transition were collected, of the GaN sample as well as of a Si sample implanted with overlapping profiles of ¹⁵¹Eu and O. The GaN spectra were fitted with two symmetric doublets, D1 and D2, with isomer shifts and quadrupole splittings of δ?=??0.27 mm/s (relative to Eu₂O₃), ΔE _Q?= 0.85 (3) mm/s; and δ?=?? 0.22 mm/s, ΔE _Q?= 2.90 (5) mm/s, respectively. D1 is attributed to Eu at substitutional Ga lattice sites; D2 to Eu at or near substitutional sites but with extensive lattice damage. The splittings of D1 and D2 correspond to quadrupole coupling frequency of 15 (2) and 50 (4) MHz, consistent with measurements of ⁶⁹Ga, ⁷¹Ga and ¹¹¹In in GaN.