High pressure mössbauer studies of magnetic actinide systems

Due to the wider radial extent of 5f electrons when compared to their 4f counterparts, intermetallics of the light actinides show a broad spectrum of magnetic properties ranging from the localized magnetism of the lanthanides to the itinerant magnetism often found in transition metal compounds. One parameter which strongly influences the magnetic character of the compound is the actinide-actinide separation which can experimentally be varied by the application of high pressure. The question of 5f electron delocalization will be reviewed with respect to Moesshauer high pressure data on NpCo₂si₂, NpAl₂, NpOs₂ and new results will be presented of NpAs. The connection of hyperfine parameters with results of X-ray diffraction studies will be discussed.Work supported by the Bundesministerium für Forschung und Technologie, Federal Republic of Germany     

Mössbauer spectroscopy with the 93 keV-resonance in67Zn

The procedures and results of high resolution Mössbauer experiments performed with the 93.3 keV resonance in absorbers of⁶⁷ZnO,⁶⁷ZnS (both wurtzite and sphalerite structures),⁶⁷ZnSe,⁶⁷ZnTe and⁶⁷ZnF₂ are reported. An essentially linear dependence between the isomer shift and the Pauling electronegativity of the ligands was found. A value of r ²=+11×10^–3 fm² is estimated. The Mössbauer parameters for both ZnS structures are equal within present limits of error. In particular, no quadrupole interaction was observed in the wurtzite modification. This indicates a nearly identical local symmetry at the Zn site in the two ZnS structures.Work supported by the Bundesministerium für Forschung und Technologie, Federal Republic of Germany and the Kernfor-schungszentrum Karlsruhe     

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.     

High resolution Mössbauer spectroscopy with67Zn in metallic systems

The high energy resolution of the 93.3 keV Mössbauer transition in⁶⁷Zn is used to investigate changes of s-electron density at the Zn nucleus in Cu-Zn alloys with special emphasis on the α-phase and on Zn-metal itself. We observe the presence of short-range order in α-brass with only four different Cu-Zn configurations, instead of the expected binomial distribution. In Zn metal, no change of center shift was observed when crossing the superconducting phase transition. The tremendous anisotropy of the Lamb-Mössbauer factor, as well as the temperature shift found for hexagonal Zn metal, demonstrate that the 93.3 keV resonance is also extremely sensitive to lattice dynamical effects. Our results, as well as specific heat data, are quantitatively described by an extended Debye model characterized by two Debye temperatures, θ_⊥ and θ_‖, which correspond to the lattice vibrations perpendicular and parallel to thec axis, respectively.     

μSR in UAs

UAs has the NaCl structure and undergoes a first order transition into a type I (single k) antiferromagnetic state at 123 K, followed by a second first order transition at 62 K into a type IA (double k) antiferromagnetic structure. μSR spectra of a powder sample were taken in zero and transverse fields up to 0.3 T. They cover the paramagnetic and the two antiferromagnetic states. The most significant features of our data are: i) a first increase of relaxation rate below T=180 K; ii) a sudden jump in both, relaxation rate and frequency shift at T=123 K, together with a small decrease in initial asymmetry (≈15%); iii) no μ⁺ spin rotation in zero field in the type I state; iv) an overlay, of 3 spectra in the type IA state. Two of these spectra show spin rotation in zero field. Their frequencies are clearly temperature dependent. In a transverse field of 5 and 10 mT the external field adds nearly fully to the internal field. Work supported in part by the Bundesministerium fur Forschung und Technologie, Federal Republic Germany.     

The pressure induced B1-B2 phase transition of alkaline halides and alkaline earth chalcogenides. A first principles investigation

In this work, we considered the pressure induced B1-B2 phase transition of AB compounds. The DFT calculations were carried out for 11 alkaline halides, 11 alkaline earth chalcogenides and the lanthanide pnictide CeP. For both the B1 and the B2 structures of each compound, the energy was calculated as a function of the cell volume. The transition pressure, the bulk moduli and their pressure derivatives were obtained from the corresponding equations of state. The transition path of the Buerger mechanism was described using roots of the transition matrix. We correlated the computed enthalpies of activation to some structure defining properties of the compounds. A fair correlation to Pearsons hardness of the ions was observed.     

Influence of the frequency and amplitude of Doppler motion on Mössbauer transmission curves

It is shown that the frequency and amplitude of Doppler motion used in Mössbauer spectroscopy may drastically influence the shape of the resonance absorption curves. If the resonance is passed in a time comparable to the lifetime of the Mössbauer state then asymmetric lines and large oscillatory overshoots are observed.