Inhomogeneous and homogeneous broadening effects onnuclear resonance experiments

Inhomogeneous broadening of resonance lines causes a reduction of absorption in nuclear resonance experiments. This is particularly devastating to the observation of the Mössbauer effect in isomers like ¹⁰⁷Ag with a half-life of 44s.It has been suggested in the literature that homogeneous broadening can provide overlap of resonance lines and thus theMössbauer effect can be recovered. The analysis presented in this paper shows that this is not the case for Mössbauer experiments, unless the radiative width Γ_Γ also increases. Although overlap occurs when the lines are homogeneously broadened to a total width Γ_{_}H which exceeds the natural width Γ, and the inhomogeneous width Δ, the Mössbauer absorption remains low because it is proportional to the factor of Γ_γ/Γ _H.     

Simple theory of superparamagnetism and spin-tunneling in Mössbauer spectroscopy

The magnetic relaxation of isolated small (< 100 Å) monodomain magnetic particles is due to superparamagnetic relaxation (predominant at high temperatures) and eventually quantum tunneling of the magnetic moment (at low temperatures). The superparamagnetic relaxation process can be formally described by an (multiple phonon absorption and emission) Orbach process with an anisotropy Hamiltonian due to crystalline or form anisotropy \widehat_Ion = S² _z and a usual dynamical spin-Hamiltonian for the spin--phonon interaction. From this Mössbauer spectra can be calculated using ab-initio or stochastic methods. Phonon-assisted tunneling and its influence on Mössbauer spectra are discussed.     

Application of 57Fe Mössbauer spectroscopy as a tool for mining exploration of bornite (Cu5FeS4) copper ore

Nuclear resonance methods, including Mössbauer spectroscopy,are considered as unique techniques suitable for remote on-line mineralogical analysis. The employment of these methods provides potentially significant commercial benefits for mining industry. As applied to copper sulfide ores, Mössbauer spectroscopy method is suitable for the analysis noted. Bornite (formally Cu₅FeS₄) is a significant part of copper ore and identification of its properties is important for economic exploitation of commercial copper ore deposits. A series of natural bornite samples was studied by ⁵⁷Fe Mössbauer spectroscopy. Two aspects were considered: reexamination of ⁵⁷Fe Mössbauer properties of natural bornite samples and their stability irrespective of origin and potential use of miniaturized Mössbauer spectrometers MIMOS II for in-situ bornite identification. The results obtained show a number of potential benefits of introducing the available portative Mössbauer equipment into the mining industry for express mineralogical analysis. In addition, results of some preliminary ^63,65Cu nuclear quadrupole resonance (NQR) studies of bornite are reported and their merits with Mössbauer techniques for bornite detection discussed.     

Experimental search for laser-induced effects in <Superscript>151</Superscript>Eu and <Superscript>57</Superscript>Fe doped crystals

We studied the Mössbauer effect in ¹⁵¹Eu and ⁵⁷Fe doped crystals in the search for laser-induced effects caused by changes in the hyperfine interaction due to electronic excitation. The Mössbauer spectra observed in the presence of laser radiation demonstrated a notable change of the shape of the ¹⁵¹Eu spectrum and the appearance of an additional hyperfine pattern in the case of the ⁵⁷Fe Mössbauer resonance.     

An57Fe Mössbauer effect study of the highT c superconductor GdBa2Cu3O7−y

Split source⁵⁷Fe Mössbauer effect spectroscopy has been performed between 4 K and 295 K on the superconducting perovskite GdBa₂Cu₃O_7?y. No evidence is seen for magnetic splitting at low temperatures as reported in some split absorder⁵⁷Fe Mössbauer experiments on this material. There is evidence for phonon mode softening, as observed for¹¹⁹Sn Mössbauer spectra of some other highT _c superconductors.     

Observation of the double optical-gamma resonance in Mössbauer spectra of 151 Eu in EuP 5 O 14 single crystal

A theoretical analysis has been made and calculation procedures have been developed for describing the hyperfine structure of ¹⁵¹Eu Mössbauer spectra and the effect of double optical-gamma resonance (DOGR) in the presence of hyperfine quadrupole interaction with an arbitrary symmetry of the electric field gradient tensor. An experimental setup was designed for DOGR-effect observation, incorporating the pumping argon laser and the tunable dye laser combined with the Mössbauer spectrometer on a common platform. The Mössbauer absorption spectra of ¹⁵¹Eu^3?+? nuclei in single crystals of europium pentaphosphate, EuP₅O₁₄, have been measured at T = 5 K and 80 K under the absence and presence of optical pumping tuned to the ⁷F $_{0}-^{5}$ D₀ electronic transition at the 578 nm wavelength. A simultaneous analysis of these spectra in terms of the spin Hamiltonian of hyperfine quadrupole interaction has allowed us to evaluate the DOGR-effect magnitude with the population of the excited (⁵D₀) electronic state under optical pumping of about 10 %.     

Polarized gamma ray investigation of iron disulphide (pyrite)

Mössbauer absorption of Fe⁵⁷, for four equivalent but differently oriented sites, in naturally occuring FeS₂ (pyrite) crystals has been studied in the ideal absorber thickness, as a function of the orientation of the crystal axes with respect to the linearly polarized gamma rays from Co⁵⁷/LiNbO₃ source and the direction of the polarization. E$\text{x}$perimental peak area ratio of ～ 1 in the polycrystalline absorber and the monocrystalline absorbers is independent of the crystal orientation. The analysis of the present experiment shows that the Mössbauer fraction, f, is isotropic and that the asymmetry parameter, η, is zero.     

Magnetic insulator glasses

An outline is given of the use of Mössbauer spectroscopy as a probe of the amorphous structure and magnetic coordination in magnetic insulator glasses. Using the⁵⁷Fe Mössbauer resonance as an example in the context of amorphous ferric oxides and fluorides, the manner in which both paramagnetic and hyperfine-field-split spectra can be analyzed is presented. Emphasis is given to the information contained in Mössbauer lineshapes and linewidths in addition to the more obvious line-position data. A number of general findings are set out for ferric speromagnetics with particular references to Mössbauer studies of amorphous Fe₂O₃, Y₃Fe₅O₁₂ (YIG), FeF₃ and NaFeF₄.     

Emission Mössbauer spectroscopic studies of57Fe atoms produced in57Co-labelled trinuclear cobalt-iron halogenoacetate complexes

Mixed-valence states of⁵⁷Fe atoms produced after EC-decay of⁵⁷Co in a series of trinuclear cobalt-iron halogenoacetate complexes, [Co^IIFe ₂ ^III O(CH_3?nX_nCO₂)₆(H₂O)₃] (0≤n≤3, X=Cl, Br, and I), were studied by comparing the results obtained by emission Mössbauer spectroscopy with those observed in absorption Mössbauer spectra of analogous trinuclear iron complexes, [Fe^IIFe ₂ ^III O(CH_3?nX_nCO₂)₆(H₂O)₃]. Some of the emission Mössbauer spectra show a temperature-dependent mixed-valence state as found in the absorption Mössbauer spectra. Others show a somewhat different temperature dependence compared with the absorption Mössbauer spectra. The results were interpreted in terms of after-effects of the EC-decay.     

Nuclear resonance reflectivity from a [57Fe/Cr]30 multilayer with the Synchrotron Mössbauer Source

Mössbauer reflectivity spectra and nuclear resonance reflectivity (NRR) curves have been measured using the Synchrotron Mössbauer Source (SMS) for a [⁵⁷Fe/Cr]₃₀ periodic multilayer, characterized by the antiferromagnetic interlayer coupling between adjacent ⁵⁷Fe layers. Specific features of the Mössbauer reflectivity spectra measured with π‐polarized radiation of the SMS near the critical angle and at the `magnetic' maximum on the NRR curve are analyzed. The variation of the ratio of lines in the Mössbauer reflectivity spectra and the change of the intensity of the `magnetic' maximum under an applied external field has been used to reveal the transformation of the magnetic alignment in the investigated multilayer.     

Mössbauer insight to metallurgy, materials science and engineering

A brief overview of the contributions which Mössbauer effect spectroscopy has made to areas of materials science is presented. A survey of the literature reveals the decreasing trends of established areas, with emergence in the past decade or so of new areas such as nanostructured materials and materials produced by mechanochemical treatment and the continuing importance of rare-earth magnetic materials. Examples of applications of ⁵⁷Fe and ¹¹⁹Sn Mössbauer spectroscopy, both transmission and backscattering, are discussed. The complementary nature of Mössbauer spectroscopy and neutron diffraction in delineation of the magnetic behaviour and structures of materials is demonstrated by the La_1?x Y _x Mn₂Si₂ series of rare-earth intermetallic compounds.     

Determination of the recoilless-fraction for57Fe in Fe3O4 by the Mössbauer Faraday effect

We have observed the Mössbauer Faraday effect in nonstoichiometric Fe₃O₄ by using a Mössbauer polarimeter. Experimental results demonstrated that electronic hopping above the Verwey temperature between Fe²⁺?Fe³⁺ ions on the octahedral sites is a localized phenomenon only and the recoilless fractions of⁵⁷Fe nuclei in Fe_3?vO₄ (v=0.02) are 0.71 for A sites and 0.62 for B sites, respectively.     

Gravitational redshift experiments with the high-resolution Mössbauer resonance in67Zn

A gravitational tedshift (GRS) experiment using the high-resolution Mössbauer resonance in⁶⁷Zn is described. The tiny Doppler motion of the source can be checked by a dc-SQUID based displacement sensor. The results on the GRS strongly indicate that solid-state effects, which are difficult to control experimentally, finally limit the accuracy that Mössbauer measurements can provide in determining the GRS. We argue that for this reason conventional Mössbauer experiments most probably will not be able to compete with other methods in future GRS measurements of very high precision.     

Electron Paramagnetic Resonance and Mössbauer Studies of Fe3+ Ions in the Fe2O3 [dbnd] MoO3 System

The electron paramagnetic resonance (EPR) and Mössbauer spectra of ironmolybdenum mixed oxides system have been investigated. Both EPR and Mössbauer measurements revealed the formation of ferric molybdate, Fe₂ (MoO₄)₃ and the existence of two different Fe³⁺ species. The EPR spectra of Fe₂ (MoO₄)₃, show two resonance lines of Fe³⁺ ions indicating that a strong exchange interaction is dominates in pure iron molybdate. Mösbauer measurements revealed that the isomer shift (I. S) increases with increasing the iron content. A maximum of quadrupole splitting (Q. S) is observed at the stoichiometric concentration corresponding to the formation of Fe₂ (MoO₄)₃. The effect of a catalytaic dehydration process on the redox behaviour of Fe³⁺ located in iron molybdate frame work is investigated. Results indicate that the catalytaic dehydration of 2-proppanol over this catalyst reduces Fe³⁺ ions to Fe²⁺ leading to the formation of the inactive phase FeMoO₄. the essential role of oxygen, in the alcohol gas feed, in regeneration the activity of the catalysts was demonstrated.     

Mössbauer spectroscopic study on (Eu1−x Gd x )FeO3

Europium gadolinium ferrites (Eu_1?xGd_x)FeO₃ (X=0, 0.2, 0.4, 0.6, 0.8) are synthesized. The results of the X-ray diffraction show that all the compounds possess a perovskite structure. Both the¹⁵¹Eu Mössbauer spectra and the⁵⁷Fe Mössbauer spectra are measured. The¹⁵¹Eu Mössbauer spectra are considered to be the pure quadrupole spectra. The results show that the isomer shift and the quadrupole splitting of the¹⁵¹Eu spectra vary with x. The hyperfine filed of the⁵⁷Fe Mössbauer spectrum depends on the unit-cell volume. The⁵⁷Fe spectra of the samples synthesised by the high-pressure and high-temperature mothod show a part of paramagnetic structure.     

Etude d'un nouveau type de fluorure antiferromagnetique a caractere bidimensionnel: NaFeF4

A new type of two-dimensional antiferromagnetic structure has been investigated by magnetic susceptibility measurements, neutron diffraction and Mössbauer resonance. The magnetic cell of NaFeF₄ is doubled along the a axis and the spins lie along the b axis. The κ^-1 vs T curve shows a sharp minimum at about 105 K close to the three-dimensional transition temperature determined by Mössbauer spectrometry (111.5 K). A calculation of z. snfc;J/kz. snfc; has been performed using a high temperature series expansions technique (J/k = -23 K). The variation of the hyperfine field in the range 0.6 ?T/T_N? 1 gave the value of the critical exponant β = 0.25.     

Investigation of the transition of acrylate cation exchangers from solidlike into highly elastic state under hydration

The transition from solid-like (glassy) state into the (elastic) state with high intramolecular mobility under hydration was investigated for two⁵⁷Fe³⁺-substituted cation exchangers (SGK ?7 and SG ?1 m with acrylic and methacrylic nature of chains). The transition was observed as sharp change of Mössbauer lineshape (appearance of quasielastic components) and decrease of Mössbauer effect probability. The region of hydration degrees in which the transition occurs in both systems varies from 1 to 3–4 H₂O molecules per ?COOH group depending on cross-linkage concentration in a nonmonotonous way.     

Experiments on the search for the effect of resonant screening on the probability of Mössbauer absorption of <Superscript>119<Emphasis Type="Italic">m</Emphasis></Superscript>Sn gamma rays

Experiments on the search for the effect of resonant screening on the Mössbauer absorption of ^119m Sn γ rays of energy 23.8 keV emitted by a standard Mössbauer Ca^119m SnO₃ γ source in the resonant SnO₂ absorber of natural isotopic composition are described. Intensities of tin γ rays and X-rays that passed through the absorber were measured with and without a resonant cylindrical screen (which was a black absorber for the 23.8-keV Mössbauer γ line) around the absorber and their ratios were calculated for each radiation separately. No difference beyond the experimental error was found between these ratios measured with the γ source both at rest and when oscillating with a frequency and amplitude enough to completely break the conditions for Mössbauer resonant absorption of 23.8-keV γ rays. The upper limit for the relative decrease, due to the influence of the resonant screen, in the intensities of these γ rays after their passing through the resonant absorber was 0.00030.     

67Zn Mössbauer study of Zn metal and Cu−Zn alloys at high pressure

A high pressure Mössbauer spectrometer for the 93.3keV resonance in⁶⁷Zn has been used to investigate Zn metal and two Cu?Zn alloys with Zn concentrations of 41.9at% and 48.0at% at 4.2K and pressures up to ～58kbar. For Zn metal the c/a-ratio plays an important role to describe the change of the Mössbauer parameters with pressure. Most striking is the increase of the recoil-free fraction by a factor of ～3. In the brass alloys a new phase is observed at 4.2K and high pressures which we tentatively identify with a martensitic α₁-phase.