Effect of pressure on the Mössbauer isomer shift and quadrupole splitting in Au(I)-cyanides

The effect of pressure on the Mössbauer isomer shift and quadrupole splitting was studied with the 77 keV resonance of¹⁹⁷Au in the Au(I)-cyanides AuCN and KAu(CN)₂ at 4.2 K under pressures up to 80 kbar. We observe an increase of the electron density and a decrease of the absolute value of the electric field gradient at the Au nuclei in both compounds with pressure. This variation is different from the correlation that has been established for these parameters within the chemical series of Au(I) compounds at ambient pressure. It indicates that the-bonding increases strongly under pressure. X-ray diffraction studies on AuCN under pressures up to 115 kbar together with investigations of the Goldanskii-Karyagin-effect on AuCN at ambient pressure support the previous assumption that the sign of the electric field gradient at the Au(I) sites is negative.     

Mössbauer study of197Au in Zn and Cd single crystals

The 77.3 keV Mössbauer transition of¹⁹⁷Au was used to study the hyperfine interactions and recoilfree fractions of dilute Au impurities in Zn and Cd single crystals at 4 K. Mössbauer sources were prepared by ion implantation of^197mHg/¹⁹⁷Hg at ambient temperature. From the quadrupole splittings the electric field gradients $$\begin{gathered} eq(Au\underline {Cd} ) = + 11.7(6) \times 10^{17} v/cm^2 and \hfill \\ eq(Au\underline {Zn} ) = ( + )15.0(2.5) \times 10^{17} v/cm \hfill \\ \end{gathered} $$ were determined. The electric field gradients as well as the isomer shifts are in good agreement with the systematics of other impurity host systems. The recoilfree fractions agree with estimates using the mass corrected Debye temperatures of the host lattice.     

Effect of pressure on the M?ssbauer isomer shift and quadrupole splitting in Au(I)-cyanides

The effect of pressure on the Mössbauer isomer shift and quadrupole splitting was studied with the 77 keV resonance of¹⁹⁷Au in the Au(I)-cyanides AuCN and KAu(CN)₂ at 4.2 K under pressures up to 80 kbar. We observe an increase of the electron density and a decrease of the absolute value of the electric field gradient at the Au nuclei in both compounds with pressure. This variation is different from the correlation that has been established for these parameters within the chemical series of Au(I) compounds at ambient pressure. It indicates that the-bonding increases strongly under pressure. X-ray diffraction studies on AuCN under pressures up to 115 kbar together with investigations of the Goldanskii-Karyagin-effect on AuCN at ambient pressure support the previous assumption that the sign of the electric field gradient at the Au(I) sites is negative.     

57Fe quadrupole splitting and isomer shift in various oxyhemoglobins: study using Mössbauer spectroscopy

A comparative study of normal human, rabbit and pig oxyhemoglobins and oxyhemoglobin from patients with chronic myeloleukemia and multiple myeloma using Mössbauer spectroscopy with a high velocity resolution demonstrated small variations of the ⁵⁷Fe quadrupole splitting and isomer shift. These variations may be a result of small structural differences in the heme iron stereochemistry of various hemoglobins.     

Uncertainty budget for determinations of mean isomer shift from Mössbauer spectra

The magnetite/maghemite content within iron oxide nanoparticles can be determined using the mean isomer shift (\(\overline {\delta }\)). However, accurate characterisation of the composition is limited by the uncertainty associated with \(\overline {\delta }\). We have identified four independent sources of uncertainty and developed a quantitative expression for the uncertainty budget. Sources of uncertainty are categorised as follows: that from the fitting of the Mössbauer spectrum (σ _fit), that of the calibration of the α-Fe reference spectrum (σ _cal), thermal corrections to the spectrum due to second order Doppler shift (SODS) (σ _Δδ ) and other experimental errors (σ _err). Each contribution is discussed in detail using ⁵⁷Fe Mössbauer spectra obtained from an iron oxide nanoparticle system at temperatures between 16 K and 295 K on different spectrometers in two different laboratories.     

A197Au Mössbauer study of the adsorption of aurocyanide onto activated carbon

The chemical state of gold adsorbed on activated carbon from solutions of KAu(CN)₂ has been studied by¹⁹⁷Au Mössbauer spectroscopy as a function of the pH and concentration of the solution, the loading of the carbon, and the drying conditions of the samples. On freshly prepared specimens Au(CN) ₂ ^? is always the dominant species. Drying leads to the formation of other forms of gold, mainly in samples loaded from strongly acidic media. An oligomeric form of AuCN is, however, also formed when samples loaded at high pH values are dried at temperatures around 100°C.     

Calibration of the isomer shift of125Te from internal conversion and mössbauer measurement

Radioactive¹²⁵I was ion-implanted into 7 different metal matrices. Al, Au, In, Pt, Sn, Te and Zn, and internal conversion and Mössbauer spectra associated with the 35.46 keV M1 transition of¹²⁵Te were measured for the same samples. A value R/R=(0.853±0.115)×10^–4 was derived for the relative difference of the nuclear charge radius for the 35.46 keV M1 transition of¹²⁵Te.     

The Mössbauer effect on 119Sn and 197Au nuclei in gold,palladium and platinum matrices

The probabilities for recoilles resonant absorption of 77.3 keV λ-rays by ¹⁹⁷Au and 23.8 keV λ-rays by ¹¹⁹Sn in matrices of gold, palladium and platinum have been calculated in the temperature ranges 4.2–100 K and 80–400 K, respectively. The calculated results show a good agreement with the experimental data.     

197Au Mössbauer study of the deactivation and reactivation of a carbon-supported AuCl 4 − hydrochlorination catalyst

Acetylene hydrochlorination catalysts consisting of activated carbon impregnated with a solution of HAuCl₄·xH₂O in aqua regia have been studied by¹⁹⁷Au Mössbauer spectroscopy. The relative amounts of AuCl ₄ ^? , of Au(0), and of an Au(J) species formed under certain process conditions were determined quantitatively. Deactivation of the catalyst at low and high temperatures was shown to be due to different mechanisms, and the reactivation of the catalyst by Cl₂ gas was studied.     

Study of the structure and electronic state of thiolate-protected gold clusters by means of 197Au Mössbauer spectroscopy

We have investigated the structures and electronic states of a series of glutathionate-protected Au clusters, Au _n (SG) _m with n = 10 ? ～55, using ¹⁹⁷Au Mössbauer spectroscopy, which allows us to probe the local environment of the constituent Au atoms via isomer shift (IS) and quadrupole splitting (QS). The spectral profile abruptly changes on going from Au₂₂(SG)₁₇ to Au₂₅(SG)₁₈, then it smoothly changes to that of Au～₅₅(SG)_m. However, the spectral profile dramatically changes on going from Au～₅₅(SG)_m to the dodecanethiolate-protected Au cluster with average diameter of 2 nm. The ¹⁹⁷Au Mössbauer spectra of glutathionate-protected Au clusters and dodecanethiolate-protected Au clusters were successfully analyzed on the basis of the structure and electronic state of Au₂₅(SG)₁₈.     

The Mössbauer effect in the points of phase transitions

The temperature dependence of the intensity of the Mössbauer line and the shift of its centre on passing through the points of phase transitions was studied. Both quantities exhibit discontinuity at transitions of the first kind while only the shift of the line centre does so at transitions of the second kind. The possibility of using the Mössbauer effect for the exact localization or even classification of phase transitions is shown.     

Aspects of the identification of iron oxidation states by Mössbauer isomer shifts

A hypothesis based on the literature data on the Mössbauer, structural, and magnetic parameters of different iron oxidation states is proposed, according to which changes in the electronic configuration of an iron ion that are caused by an electron (or a change of iron oxidation state by one) can vary the isomer shift by a constant (~0.33 mm s^?1), if it is assumed that the structure of the iron’s valent shell and iron spatial environment remain unchanged.     

Mössbauer effect and XRD studies of iron-zinc binary alloys

Mössbauer spectroscopy and XRD were employed to characterize the microstructural properties of iron-zinc binary alloys between 0–31 at.% Fe. Samples were prepared with accuracies of ±0.5 at.% Fe, and the Mössbauer and lattice parameters were monitored as a function of iron concentration across each phase. Two iron sites were observed in the phase (18–31 at.% Fe), whose occupancies and isomer shifts varied continuously with iron content. However, the quadrupole splitting of each site remained constant. Within the ₁ phase (19–24 at.% Fe), three iron sites were observed whose isomer shifts and quadrupole splittings remained constant, while their occupancies varied with iron concentration. For the first time, a third iron site was observed in the phase (8–13 at.% Fe), whose occupancy increases with iron content. Also, the site occupancies of the two other sites appear to remain constant, while other Mössbauer parameters vary continuously with iron content. Analysis of the phase (6–7 at.% Fe) showed the presence of one iron site, whose parameters were not observed to change due to the small variance in iron concentration. XRD studies indicate the lattice parameters across the and phases vary continuously with iron concentration. Moreover, a better understanding of these phases, as formed in galvanneal steel coatings, was obtained.Research supported by the International Lead Zinc Research Organization, Inc., Grant No. ZM-403 and Virginia's Center for Innovative Technology, Grant No. MAT-92-007-01.     

Structural evolution of glutathionate-protected gold clusters studied by means of 197 Au Mössbauer spectroscopy

¹⁹⁷Au Mössbauer spectra of a series of glutathionate-protected gold clusters, Au _n (SG) _m , with n = 10 ? ~55, were re-analyzed to understand the structure evolution behavior. The numbers of gold atoms coordinated by different numbers (0, 1, and 2) of the GS ligands were successfully determined by assuming individual isomer shifts and quadrupole splittings for the three sites in Au₂₅(SG)₁₈ (Tsukuda et al., Chem Lett 40:1292, 2011). The analysis revealed the drastic structural evolution of Au _n (SG) _m in the range of n = 10 ? ~55. In Au₁₀(SG)₁₀, all the gold atoms are bonded to GS ligands, indicating –Au–S(G)– cyclic structures. A catenane structure was proposed for Au₁₀(SG)₁₀. At n = 25, a single Au atom without the GS ligation appeared, consistent with the formation of an icosahedral Au₁₃ core protected by six staples, –S(G)–[Au–S(G)–]₂. At n = 39, it is considered that Au₃₉(SG)₂₄ has a similar structure to that of Au₃₈(SC₂H₄Ph)₂₄ with face-fused bi-icosahedral Au₂₃ core.     

Determination of relative force constant inβ-Ti (Fe) alloys by means of the Mössbauer second-order Doppler shift

In the present work we have used the Mössbauer effect to investigate the dependence of the second-order Doppler shift on temperature for one sample of-Ti (Fe) alloy with 9.3 at.% Fe. The experimental data of total shift of the Mössbauer line in a temperature interval between 4K and 975 K were fitted to theoretical expressions obtained by assuming the Debye approximation to describe the lattice and a more general approximation for high temperature, which take into account the difference in mass of the impurity atom and that of the host lattice. From the fitting we have obtained that the Ti-Fe interatomic forces are larger than that of Ti-Ti.At the time this work was done E. Galvão da Silva was with the Universität des Saarlandes, Angewandte Physik, D-6600 Saarbrücken, F. R. Germany, as a Fellow on Training Program of the IAEA/Vienna and CNEN/Brazil     

Nutations of magnetizations of sublattices and their role in the formation of Mössbauer spectra of antiferromagnetic nanoparticles

A law determining the dispersion shift of the anti-Stokes band of the supercontinuum of a light bullet in a filament of a femtosecond laser pulse in transparent dielectrics has been established. The dispersion equation theoretically obtained for the anti-Stokes shift has been confirmed by spectroscopic studies of the filamentation of the near and middle infrared ranges in fused silica and fluorides.     

Mössbauer spectroscopy study of the disordering process of Fe-rich FeAlSi alloys

In this work we study systematically the influence of different Al/Si ratios on the magnetic and structural properties of mechanically disordered powder Fe₇₅Al_25?x Si _x , Fe₇₀Al_30?x Si _x and Fe₆₀Al_40?x Si _x alloys by means of Mössbauer spectroscopy and X-ray diffraction measurements. In order to obtain different stages of disorder the alloys were deformed by ball milling annealed (ordered) alloys during different number of hours. X-ray and Mössbauer data show that mechanical deformation induces the disordered A2 structure in these alloys. The results indicate that addition of Si to binary Fe–Al alloys makes the disordering more difficult. The study of the hyperfine fields indicates that depending on the Fe content the magnetic behaviour of these ternary alloys varies. For Fe₇₅Al_25?x Si _x series, the alloys have different magnetic behaviours with deformation depending on the Si content. The magnetization of the alloys with high Si content decreases with deformation, as it happens to binary Fe₇₅Si₂₅ and the magnetization of the alloys with low Si content increases with deformation, as it happens to binary Fe₇₅Al₂₅. For Fe₇₀Al_30?x Si _x series the mean hyperfine fields show that there are two different stages with the disordering, in a first stage the mean hyperfine fields decrease and in the second stage they increase. Finally, for Fe₆₀Al_40?x Si _x alloys there is a magnetic transition, from a paramagnetic ordered state to a magneticdisordered state.