Vibrations and Phase Stability in Mixed Valence Antimony Oxide.

α-Sb2O4 (cervantite) and ß-Sb2O4 (clinocervantite) are mixed valence compounds with equal proportions of SbIII and SbV as represented in the formula SbIIISbVO4. Their structure and properties can be difficult to calculate owing to the SbIII lone-pair electrons. Here, we present a study of the lattice dynamics and vibrational properties using a combination of inelastic neutron scattering, Mössbauer spectroscopy, nuclear inelastic scattering, and density functional theory (DFT) calculations. DFT calculations that account for lone-pair electrons match the experimental densities of phonon states. Mössbauer spectroscopy reveals the ß phase to be significantly harder than the α phase. Calculations with O vacancies reveal the possibility for nonstoichiometric proportions of SbIII and SbV in both phases. An open question is what drives the stability of the α phase over the ß phase, as the latter shows pronounced kinetic stability and lower symmetry despite being in the high-temperature phase. Since the vibrational entropy difference is small, it is unlikely to stabilize the α phase. Our results suggest that the α phase is more stable only because the material is not fully stoichiometric.

New Measurement Resolves Key Astrophysical Fe XVII Oscillator Strength Problem.

One of the most enduring and intensively studied problems of x-ray astronomy is the disagreement of state-of-the art theory and observations for the intensity ratio of two Fe XVII transitions of crucial value for plasma diagnostics, dubbed 3C and 3D. We unravel this conundrum at the PETRA III synchrotron facility by increasing the resolving power 2.5 times and the signal-to-noise ratio thousandfold compared with our previous work. The Lorentzian wings had hitherto been indistinguishable from the background and were thus not modeled, resulting in a biased line-strength estimation. The present experimental oscillator-strength ratio R_{exp}=f_{3C}/f_{3D}=3.51(2)_{stat}(7)_{sys} agrees with our state-of-the-art calculation of R_{th}=3.55(2), as well as with some previous theoretical predictions. To further rule out any uncertainties associated with the measured ratio, we also determined the individual natural linewidths and oscillator strengths of 3C and 3D transitions, which also agree well with the theory. This finally resolves the decades-old mystery of Fe XVII oscillator strengths.

Mössbauer, Nuclear Forward Scattering, and Raman Spectroscopic Approaches in the Investigation of Bioinduced Transformations of Mixed-Valence Antimony Oxide.

Mössbauer spectroscopy, nuclear forward scattering, and Raman spectroscopy were applied to study redox transformations of the synthesized mixed-valence (III/V) antimony oxide. The transformations were induced by a culture of a hyperthermophilic archaeon of the genus Pyrobaculum. The applied methods allowed us to reveal the minor decrease of ca. 11.0 ± 1.2% of the antimony(V) content of the mixed-valence oxide with the concomitant increase of antimony(III). The method sensitivities for the quantitative assessment of the Sb(III/V) ratio have been considered.

High Resolution Photoexcitation Measurements Exacerbate the Long-Standing Fe XVII Oscillator Strength Problem.

For more than 40 years, most astrophysical observations and laboratory studies of two key soft x-ray diagnostic 2p-3d transitions, 3C and 3D, in Fe XVII ions found oscillator strength ratios f(3C)/f(3D) disagreeing with theory, but uncertainties had precluded definitive statements on this much studied conundrum. Here, we resonantly excite these lines using synchrotron radiation at PETRA III, and reach, at a millionfold lower photon intensities, a 10 times higher spectral resolution, and 3 times smaller uncertainty than earlier work. Our final result of f(3C)/f(3D)=3.09(8)(6) supports many of the earlier clean astrophysical and laboratory observations, while departing by five sigmas from our own newest large-scale ab initio calculations, and excluding all proposed explanations, including those invoking nonlinear effects and population transfers.

Insights from 125Te and 57Fe nuclear resonance vibrational spectroscopy: a [4Fe-4Te] cluster from two points of view.

Iron-sulfur clusters are common building blocks for electron transport and active sites of metalloproteins. Their comprehensive investigation is crucial for understanding these enzymes, which play important roles in modern biomimetic catalysis and biotechnology applications. We address this issue by utilizing (Et4N)3[Fe4Te4(SPh)4], a tellurium modified version of a conventional reduced [4Fe-4S]+ cluster, and performed both 57Fe- and 125Te-NRVS to reveal its characteristic vibrational features. Our analysis exposed major differences in the resulting 57Fe spectrum profile as compared to that of the respective [4Fe-4S] cluster, and between the 57Fe and 125Te profiles. DFT calculations are applied to rationalize structural, electronic, vibrational, and redox-dependent properties of the [4Fe-4Te]+ core. We herein highlight the potential of sulfur/tellurium exchange as a method to isolate the iron-only motion in enzymatic systems.

Strong higher-order resonant contributions to x-ray line polarization in hot plasmas.

We studied angular distributions of x rays emitted in resonant recombination of highly charged iron and krypton ions, resolving dielectronic, trielectronic, and quadruelectronic channels. A tunable electron beam drove these processes, inducing x rays registered by two detectors mounted along and perpendicular to the beam axis. The measured emission asymmetries comprehensively benchmarked full-order atomic calculations. We conclude that accurate polarization diagnostics of hot plasmas can only be obtained under the premise of inclusion of higher-order processes that were neglected in earlier work.