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The effect of coating with nine different carboxylic acids (glycolic, propionic, lactic, malic, tartaric, citric, mandelic, caproic and caprylic) on nanostructured magnetite (D ~ 10 nm) was studied by Raman and photoacoustic, magnetic and 57Fe Mossbauer measurements. Mossbauer spectra of frozen suspensions showed dominantly magnetically split envelopes at lower temperatures, which were evaluated by hyperfine field distribution method. Mossbauer and Raman spectroscopy indicated similar variation of relative occurrence of magnetite and maghemite phases. These results are discussed on the basis of the hypothesis that different carboxylic acids can promote either the oxidation or reduction of iron oxide nanoparticles.

Frozen aqueous solution of hyperalkaline tin(II)-hydroxide was analysed by 119Sn Mossbauer spectroscopy at low temperature in order to determinate the structure of the hydroxo complex formed under hyperalkaline (pH > 13) conditions. Interestingly, the quadrupole doublet characteristic of this complex in the 119Sn Mossbauer spectrum exhibited asymmetry in the line intensities. Analysis of the temperature dependence of the Mossbauer spectra demonstrated that this phenomenon can be rationalised by the Goldanskii–Karyagin effect. The effect emerges due to the vibrational anisotropy of bonds in the tin complex formed in hyperalkaline solution, similarly to what has been found earlier for SnF2 with analogous Sn bond structure.

A series of novel [Fe(MeiPrGlyoxH)2(amine)2] complexes have been synthesized [(MeiPrGlyoxH2 = methylisopropylglyoxime, amine = 3,5-dimethylpyridine, 4-(dimethylamino)pyridine, 4-(phenylamino)phenol, 2-imidazolidone)] and characterized by 57Fe Mossbauer, FTIR, UV–Vis spectroscopy, mass spectrometry, AFM and thermoanalytical methods. Quantum chemical (DFT) computations of [Fe(MeiPrGlyoxH)2(3,5-dimethyl-Py)2] (Py = pyridine) complex were also performed. The square-planar structure of [Fe(MeiPrGlyoxH)2] moiety is similar to that of [Fe(MeEtGlyoxH)2]. The incorporation of branching alkyl chains (isopropyl) in the complexes alters the Fe–N bond length and results in high-spin iron(II) state.

Liquids trapped in the pores of certain silicate glasses (such as Corning Vycor ‘thirsty’ glass) were found to display frozen solutions like behavior at temperatures much higher than their actual freezing point. For example, recoilless γ-resonance absorption was observed for Mossbauer active solutes such as 119Sn and 57Fe salts at room temperature (i.e., without the need of quenching). Thus capillary Mossbauer spectroscopy (CMS) proved to be a new and useful experimental tool with great potential in solution chemistry. As part of a research project concerned with the hydrolysis of SnII salts, we attempted to perform 119Sn CMS measurements for solutions containing stannous ion in a range of aqueous environments. Somewhat surprisingly, we found that under ambient conditions, SnII aqueous liquid solutions, both the acidic and the basic systems, are essentially CMS-silent. This can be attributed to the strong temperature dependence of Lamb–Mossbauer factor of SnII species, which may result in the complete disappearance of Mossbauer pattern well below room temperature. These observations can also explain why previous publications concerned with the use of CMS dealt exclusively with SnIV and not with SnII containing liquids.

Thin films prepared by vacuum evaporation of 57Fe and subsequent low energy ion implantation were investigated by conversion electron Mossbauer spectroscopy and AFM measurements. A sextet with Mossbauer parameters of δ = 0.1 mm/s and B = 26 T appearing in the CEM spectra was identified as amorphous iron. Passivation and phosphonation of the thin films revealed the high affinity of amorphous iron in chemical reactions.

In this paper we present 57Co emission Mossbauer and AC magnetic susceptibility studies of La0.8Sr0.2CoO3-δ perovskite. The observed coexistence of paramagnetic and magnetic subspectra in the 57Co emission Mossbauer spectra, as well as the difference of their isomer shifts support the existence of electronic phase separation in this perovskite, in good agreement with the double exchange based cluster model.

Mossbauer spectroscopic studies were carried out in acidic (pH 2.3) 57FeIII nitrate containing aqueous solutions of indole-3-butyric acid (IBA), rapidly frozen in liquid nitrogen at various periods of time after mixing the reagents. The data obtained show that in solution in the presence of IBA, iron(III) forms a complex with a dimeric structure characterised by a quadrupole doublet, whereas without IBA under similar conditions iron(III) exhibits a broad spectral feature due to a slow paramagnetic spin relaxation which, at liquid nitrogen temperature, results in a large anomalous line broadening (or, at T = 4.2 K, in a hyperfine magnetic splitting). The spectra of 57FeIII+IBA solutions, kept at ambient temperature under aerobic conditions for increasing periods of time before freezing, contained a gradually increasing contribution of a component with a higher quadrupole splitting. The Mossbauer parameters for that component are typical for iron(II) aquo complexes, thus showing that under these conditions gradual reduction of iron(III) occurs, so that the majority (85%) of dissolved iron(III) is reduced within 2 days. The Mossbauer parameters for the iron(III)-IBA complex in aqueous solution and in the solid state (separated from the solution by filtration) were found to be similar, which may indicate that the dissolved and solid complexes have the same composition and/or iron(III) coordination environment. For the solid complex, the data of elemental analysis suggest the following composition of the dimer: [L2Fe-(OH)2-FeL2] (where L is indole-3-butyrate). This structure is also in agreement with the data of infrared spectroscopic study of the complex reported earlier, with the side-chain carboxylic group in indole-3-butyrate as a bidentate ligand. The Mossbauer parameters for the solid 57FeIII-IBA complex at T = 80 K and its acetone solution rapidly frozen in liquid nitrogen were virtually identical, which indicates that the complex retains its structure upon dissolution in acetone.

Nine complexes of adenosine and related compounds (adenosine-5'-monophosphate, adenosine-5'-triphosphate, 1-methyl-adenosine, pyridoxal-5-phosphate and β-nicotinamide-adenine-dinucleotide-phosphoric acid) with di-n-butyltin(IV) oxide and/or di-n-butytin(IV) dichloride were prepared in the solid state. The compositions of the complexes were determined by standard analytical methods. It was found that the complexes contain organotin(IV) moiety and the ligand in a ratio of 1:1 or 2:1. The FTIR spectra demonstrated that di-n-butyltin(IV) oxide reacts with the D-ribose moiety of the ligands, while di-n-butyltin(IV) dichloride is co-ordinated to the deprotonated phosphate group. The basic part of the ligands does not participate directly in complex formation. Comparison of the experimental Mossbauer QS values with those calculated on the basis of the PQS concept revealed that the organotin(IV) moiety has trigonal-bipyramidal, octahedral and in some cases tetrahedral geometry also. Some of the complexes contain the organotin(IV) cation in two different surroundings.

57Fe transmission Mossbauer spectroscopy and X-ray diffractometry were used to study clay mineral samples originated from two different regions (Um-arrazm and Alkawasim) of Libya in order to get information about their mineralogical composition to assess their potential for use in the Libyan oil industry. In the samples originated from Um-arrazm calcite, akaganeite and nontronite while in the samples originated from Alkawasim quartz, akaganeite, montmorillonite, kaolinite, illite, mica and hematite were identified with different ratios by using diffraction method. The differences in the phase composition of iron-containing phases of samples from different localities have reflected in the complex Mossbauer spectra at both 300 K and 80 K. For the samples originated from Um-arrazm the Mossbauer parameters of subspectra were identified as nontronite and akaganeite.

57Fe Mossbauer spectroscopy measurements were performed on the perovskite compounds Eu0.7Pr0.3Ba2(Cu0.9957Fe0.01)3O7-δ, EuBa1.5Pr0.5(Cu0.9957Fe0.01)3O7-δ and EuBa1.3Pr0.7(Cu0.9957Fe0.01)3O7-δ. The observed 57Fe Mossbauer spectra provided an evidence for the correct site assignment of subspectra originating from 57Fe in different microenvironments. Apart from a minor component which was assigned to the 57Fe in the Cu(2) site of the copper oxide plane, all the subspectra could be attributed to the 57Fe in the Cu(1) copper oxide chain site with a fourfold (doublet D1), fivefold (doublet D2) or sixfold (doublet D3) oxygen coordination. In contrast, in the compound EuBa2(Cu0.9957Fe0.01)3O7-δ the 6-coordinated (D3) species has not been observed. The substitution of Pr for Eu or for Ba resulted in an increased occupancy of the O(5) antichain oxygen sites, which was explained by the charge neutrality criterion. Especially, the replacement of Ba2+ with Pr3+ led to an unusually high degree of occupancy of O(5) sites. In the 57Fe Mossbauer spectra the relative area of the 6-coordinated species (D3) increased, and that of the 4-coordinated one (D1) vanished completely in the case when Pr was substituted for Ba. Furthermore, the proportion of the 6-coordinated (D3) species increased at the expense of the 5-coordinated (D2) one with an increasing concentration of Pr at the Ba site. These experimental results are consistent with the variety of Mossbauer results reported so far.

Sediments from the Admiralty Bay, King George Island, Antarctica, were investigated by 57Fe Mossbauer spectroscopy, X-ray diffractometry, and radiometry. Quartz, feldspar, chlorite, calcite, dolomite, mica, kaolinite, hematite and magnetite were identified as constituent minerals in the sediment samples. The phase composition and the iron distribution among the crystallographic sites of iron-bearing minerals (silicates, magnetite and hematite) of samples from different location have been derived from the complex Mossbauer spectra. At different locations sediments had significant characteristic differences in the mineral composition, in the iron distribution among the crystallographic site of silicates, and in the specific radioactivity of Cs radionuclides. These results indicate differences in the rock formation and alteration by the sediments in this maritime part of Antarctica. There is a much higher amount of iron oxides in the sediments from south part of the geological fault across the Admiralty Bay than in the north part. This can be associated with much more alteration in the rocks in the south part compared to the northern one. This finding can contribute to the question of the history of the formation and alteration of volcanic rocks in the border of Antarctica.

The paper offers three applications of nuclear methods in the research of chemical structure. First, progress in positron annihilation spectroscopy is illustrated by a positron beamline study, which obtained results that are not available through conventional experiments. The positron beam was used for the study of Langmuir-Blodgett (LB) films containing 4-58 layers of arachidic acid and its salts. These measurements have shown that this emerging technique is capable of characterizing even such elusive systems. Second, the potential of Mossbauer spectroscopy to answer current challenges of solid state chemistry are shown in a study on perovskites of recent interest. 151Eu Mossbauer spectroscopy was used to study the effect of Pr substitution in EuBa2Cu3O7-δ. It was shown that the introduction of Pr into the rare earth site as well as into the Ba site results in the appearance of extra electrons both in the copper oxide planes and at the 4f shell of Eu cations. The observed effects were explained by the hole filling effect of Pr. Finally, a survey is presented on the recently developed techniques for nuclear resonant scattering of synchrotron radiation, an exciting and very rapidly developing extension to conventional Mossbauer spectroscopy. An interesting new result is that nuclear inelastic scattering experiments performed on solutions of 57Fe complexes show contribution from vibrations rather than from diffusion to the inelastic spectra.

Mossbauer, FTIR and XRD analyses showed that in aqueous medium in air in the presence of L-tryptophan (Trp) or indole-3-acetic acid (IAA) the ambient-temperature ageing of the precipitates formed from ferrous sulphate at pH∼7 gave composite phases with varying proportions of γ-FeOOH (a dominating crystalline phase), α-FeOOH (both fine-grained, showing superparamagnetic behaviour at 298 K, and relatively better crystallized) and amorphous ferric hydroxide. The experimental data suggested a competition for adsorption sites at the oxyhydroxide surface in the suspension during phase transformations, as well as the transformation of γ-FeOOH (and/or amorphous ferric hydroxide) to α-FeOOH via the dissolution-reprecipitation mechanism. The formation of certain ferric oxyhydroxide phases in the presence of Trp and IAA — released e.g., in the course of bacterial and plant metabolism — can contribute to the regulation of soil mineral composition.

57Fe and 151Eu Mossbauer spectroscopy as well as RF susceptibility measurements were applied to study the effects of Pr substitution either into the rare earth or into the Ba site in Eu1−x Pr x Ba2Cu3O7−δ and EuBa2−x Pr x Cu3O7−δ, respectively. Site mixing of Pr between the rare earth and Ba sites could be excluded by the utilization of 57Fe Mossbauer spectroscopy. It was found that there exists a correlation between the 151Eu isomer shift and the onset temperature of the superconducting transition independent of the location of Pr. RF susceptibility measurements provide an evidence for a difference in the magnetic moment of Pr substituted for the Eu or Ba sites. The obtained results can be explained by hole filling as the dominant effect of Pr substitution.

A real specimen originating from the primary circuit of a VVER-440 type pressurized water cooled nuclear reactor has been studied by Conversion Electron Mossbauer Spectroscopy (CEMS) in order to find out how the AP-CITROX decontamination procedure modifies the structure and composition of the surface oxide layer of stainless steel which is used in the steam generator. Other methods like voltammetry, gravimetry, and SEM-EDAX were also applied to characterize the samples and to help the interpretation of CEMS results. It was found that, in contradiction with expectations, the presence of the surface magnetite layer could not be convincingly identified even on the non-decontaminated sample. This finding together with the relatively weak Mossbauer signals indicated that the surface oxide layer is strongly Fe-depleted. It was also concluded that the upper layer of the bulk steel (under the oxide layer) has an altered composition probably due to irradiation-enhanced diffusion of the metallic constituents. It was established that the AP-CITROX decontamination procedure does not exert detrimental effects on the thickness and composition of the surface oxide layer.

151Eu Mossbauer spectrum of IR-transmitting calcium aluminate glass, 60CaO·32Al2O3·5Fe2O3·3Eu2O3, consists of a broad peak due to distorted Eu(III) with δ and Δ values of 0.91 and −2.02 mm·s−1, respectively. Debye temperatures (θD) of 360 and 320 K were obtained from the temperature dependence of absorption area (A) and that of δ, respectively. These θD values indicate that Eu(III) atoms occupy substitutional sites of distorted Al(III)O4 tetrahedra in calcium aluminate glass. The δ value of 0.62 mm/s obtained from the heat-treated sample (glass ceramic) indicates that Eu(III)-O bonds became less covalent. A smaller Δ value of −1.20 mm·s−1 was obtained for Eu(III) in the glass ceramic, indicating less distorted Eu(III)O4 tetrahedra.

119Sn conversion electron Mossbauer spectroscopy, X-ray diffractometry and energy dispersive X-ray analysis (EDAX) were employed to investigate microstructure, composition and phases present in as-electroplated Sn-Cr and Sn-Cr-Zn alloys deposited on copper substrates. In the Sn-Cr deposits Cu, β-Sn, Cr-Sn phases can be identified by X-ray diffractometry. The phase composition is significantly different between the samples prepared with relatively higher and lower current densities. In the diffractograms of Sn-Cr-Zn deposits Cu, β-Sn, Zn phases can be well identified. A small intensity amorphous peak is also present, which can perhaps be associated with the presence of some amorphous Zn and Sn alloy. 119Sn Mossbauer spectra of Sn-Cr deposits exhibit an asymmetric broad main line centered near the isomer shift characteristic of β-Sn as well as they contain a small component near the zero velocity which can be attributed to a SnO2 phase based upon its characteristic. 119Sn Mossbauer spectra of Sn-Cr-Zn deposits are roughly similar to those of Sn-Cr deposits although the Mossbauer parameters of the third phase are different and vary with the Zn content. The presence of SnO2 on the surface mainly in the Sn-Cr samples can be attributed to the corrosion process in the air.

Traditional black pottery produced in Nadudvar, E-Hungary, was studied by 57Fe Mossbauer spectroscopy, X-ray diffractometry and microscopy. Quartz, feldspar, clay minerals (kaolinite, smeetite, illite) and calcite were identified in the basic clay material by X-ray diffractometry (XRD). Mossbauer spectroscopy (MS) of the original clay revealed that about 35% of iron compounds were present in goethite while the rest in clay minerals (illite and smectite). After firing the clay in air using an electric furnace (red pottery is prepared in the same way), the Mossbauer spectra showed hematite as the only iron oxide or hydroxide phase, being in good agreement with X-ray diffractometry. In the black product itself, fired in the traditional open-flame furnace, the Mossbauer spectra reflected the presence of iron in magnetite and in sheet silicates with approximately the same relative ratio of oxides and silicates as in the starting material. This can be interpreted as a result of the transformation of goethite to hematite in the first step of firing (in air), and as a reduction of hematite to magnetite in the second step of firing (closed from air). A significant difference was found in the distribution of iron at the Fe2+ and Fe3+ cation sites in the black surface (more Fe2+) and at the dark gray bulk of the fired pottery (less Fe2+), showing that the reduction of Fe3+ occurs in the silicates instead of further reduction of the magnetite (e.g., to wustite).

Introduction of the Mossbauer nuclei 57Fe into Hg-1223 phase and that of 57Fe and 151Eu into Tl-1212 and Tl-1223 superconductors were investigated. Samples of high phase purity were obtained. Scanning electron microscopy and optical microscopy in normal and polarized light were employed to study the microstructure of the specimens. Energy dispersive X-ray analysis showed that 57Fe in the Hg-based samples and 57Fe as well as 151Eu in the Tl-based compounds, entered superconducting phases. Incorporation of Eu3+ into the superconducting phase favored the formation of the Tl-1212 phase. Mossbauer spectroscopy showed that Eu3+ entered the Ca-site. Two doublets found in the 57Fe Mossbauer spectra in both the Hg-1223 and the Tl-1223 phase referred to two different micro-environments of Fe3+. The assignment of the 57Fe Mossbauer spectra was made under the assumption that Fe favored the 1223 phase. Fe3+ may replace Cu in both the square pyramidal, five-fold oxygen coordinated Cu sites between the Ca and Ba-(Sr)-O layers, and in the square planar, four-fold oxygen coordinated Cu sites the Ca layers in the superconducting phases in both the Hg- and the Tl-based materials. From the relative areas of the two doublets, we concluded that the Fe3+ preferred the square planar Cu site.

Triphenyltin(IV) complexes ofN-acetylglycine,N-acetyl-L-leucine,N-acetyl-L-asparagine andN-acetyl-L-tyrosine were prepared by two methods and characterized by means of different spectroscopic methods (FTIR, multinuclear,1H,13C and119Sn NMR and119Sn Mossbauer). The spectroscopic data indicated that theN-acetylglycine complex adopts a trigonal-bipyramidal structure in which the monodentate carboxylate and the amide-C=O group are bound to the same organotin(IV) moiety. The other three complexes are linear oligomers in which the planar Ph3Sn(IV) is coordinated axially by a monodentate carboxylate and an amide-C=O from two different ligands. At theC-terminal end of the oligomer chain there is a tetracoordinated tin(IV) with a monodentate carboxylate as donor group.

Eight di-n-butyltin(IV) complexes with glycolic, 2-hydroxy-propionic, succinic and malic acids, have been prepared by two different procedures. The compounds were characterised by elemental analysis, FTIR, Raman and119Sn Mossbauer spectroscopy. The IR and Raman data indicated the presence of bidentate and/or monodentate carboxylate groups, non linear C−Sn−C bonds, and Sn−O bonds within the complexes. The results of Mossbauer spectroscopic measurements, based on point-charge model calculations, have shown the occurrence of trigonal bipyramidal environment in the central tin(IV) atom, besides the octahedral and tetrahedral structure.

57Fe Mossbauer spectroscopy was used to study the effects of heavy ion irradiation on (Bi0.93Pb0.17)Sr1.9Ca2.05(Cu1.02Fe0.01)3Oy superconductors. The Mossbauer spectra of the irradiated superconductor showed significant changes in the subspectra belonging to different Cu microenvironments into which Fe ions were substituted. The relative occurrence of Fe occupying the square pyramidal fivefold oxygen coordinated Cu sites decreased while Fe3+ substituting the square planar fourfold oxygen coordinated Cu sites increased upon bombardment by 246 MeV 86Kr8+ ions. This observation was interpreted on the basis of partial replacement of the apical oxygen atoms in the square pyramids surrounding one of the Cu sites. Such oxygen vacancies create additional square planar coordination sites for Cu. These results also support the covalent character of Cu-O bonds in the superconducting layer as well as the ionic character of bond of apical oxygen to Cu.

151Eu and 141Pr Mossbauer spectroscopy was applied to study the effects of Pr substitution for Eu or Ba atoms in Eu1-xPrxBa2Cu3O7-δ and EuBa2-xPrxCu3O7-δ, respectively. It was found that there exists a correlation between the 151Eu isomer shift and the onset temperature of the superconducting transition, independent of the location of Pr. This shows that the extra electrons provided by the Pr increase the electronic density in the copper oxide planes and in the 4f orbitals of Eu31, simultaneously. The polycrystalline compound EuBa1.3Pr0.7Cu3O7-δ has been investigated by 141Pr Mossbauer spectroscopy. The observed 141Pr isomer shift, δ(4.2 K) = 0.10(15) mm/s relative to PrF3, reflects a valence state of 3+ for the Pr located at the Ba site in EuBa1.3Pr0.7Cu3O7-δ, being in contrast to the valence state of 3.4+ found earlier for Pr which was situated at the rare earth site. This means that the valence state of Pr substituted for Eu is different from that of Pr substituted for Ba. These results suggest that the suppression of superconductivity by Pr substituted for the rare earth atoms is a consequence of the hole filling effect.

151Sn Mossbauer spectroscopy was performed with tin triflate Sn(OTf)2 in order to determine its Mosbauer parameters for analytical purposes. The typical Mossbauer parameters at 80 K for crystalline Sn(OTf)2 are IS=4.01±0.02 mm/s and QS=1.20±0.04 mm/s and show that the stannous ion is at a site with less than cubic symmetry under perturbation of the crystal field effect.