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Energy shift of Fe-K fluorescence lines due to low ionization demonstrated with XRISM in Centaurus X-3

The Fe K$\alpha$ fluorescence line at 6.4 keV is a powerful probe of cold matter surrounding X-ray sources and has been widely used in various astrophysical contexts. The X-ray microcalorimeter spectrometer onboard XRISM can measure line shifts with unprecedented precision of ${\sim }$0.2 eV, equivalent to a line-of-sight velocity of ${\sim }$10 km s$^{-1}$. At this level of accuracy, however, several factors that influence the line energy must be carefully considered prior to astrophysical interpretation. One such important factor is the ionization degree, Fe$^{q+}$. The K$\alpha$ line shifts redward by ${\sim }$4 eV as q increases from 0 (neutral) to 8 (Ar-like). Additionally, the accompanying Fe K$\beta$ line at 7.06 keV shifts blueward by ${\sim }$30 eV from $q=0$ to 8. We demonstrate that this effect is actually observable in the XRISM data of the high-mass X-ray binary Centaurus X-3 (Cen X-3). We advocate that the differential energy shift between the K$\alpha$ and K$\beta$ line provides a robust estimate of q by decoupling from other effects that shift the two lines in the same direction. We derived $q \sim 5$ (Sc-like) for the fluorescing matter by comparing the observation with atomic structure calculations of our own and in the literature. By accounting for the derived charge state and the corresponding shift in the rest-frame line energy, we made corrections for this effect and reached a consistent residual shift among the K$\alpha$, K$\beta$, and the optical measurement attributable to the systemic velocity of the system. Consequently, we obtained a new constraint on the location of the cold matter. This ionization effect needs to be assessed in all use cases of the Fe K$\alpha$ line shift beyond Cen X-3, and the proposed metric is generally applicable to all of them.

Astronomy and AstroPhysics↗

Ligand Noninnocence in Iron Corroles: Insights from Optical and X-ray Absorption Spectroscopies and Electrochemical Redox Potentials

Two new series of iron meso-tris(para-X-phenyl)corrole (TpXPC) complexes, Fe[TpXPC]Ph and Fe[TpXPC]Tol, in which X=CF 3 , H, Me, and OMe, and Tol=p-methylphenyl (p-tolyl), have been synthesized, allowing a multitechnique electronic–structural comparison with the corresponding FeCl, FeNO, and Fe 2 (μ-O) TpXPC derivatives. Optical spectroscopy revealed that the Soret maxima of the FePh and FeTol series are insensitive to the phenyl para substituent, consistent with the presumed innocence of the corrole ligand in these compounds. Accordingly, we may be increasingly confident in the ability of the substituent effect criterion to serve as a probe of corrole noninnocence. Furthermore, four complexes—Fe[TPC]Cl, Fe[TPC](NO), {Fe[TPC]} 2 O, and Fe[TPC]Ph—were selected for a detailed XANES investigation of the question of ligand noninnocence. The intensity-weighted average energy (IWAE) positions were found to exhibit rather modest variations (0.8 eV over the series of corroles). The integrated Fe-K pre-edge intensities, on the other hand, vary considerably, with a 2.5 fold increase for Fe[TPC]Ph relative to Fe[TPC]Cl and Fe[TPC](NO). Given the approximately C 4v local symmetry of the Fe in all the complexes, the large increase in intensity for Fe[TPC]Ph may be attributed to a higher number of 3d holes, consistent with an expected Fe IV -like description, in contrast to Fe[TPC]Cl and Fe[TPC](NO), in which the Fe is thought to be Fe III -like. In conclusion, these results afford strong validation of XANES as a probe of ligand noninnocence in metallocorroles. Electrochemical redox potentials, on the other hand, were found not to afford a simple probe of ligand noninnocence in Fe corroles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetic moment evolution and spin freezing in doped BaFe2As2

Fe-K β X-ray emission spectroscopy measurements reveal an asymmetric doping dependence of the magnetic moments μ bare in electron- and hole-doped BaFe 2 As 2 . At low temperature, μ bare is nearly constant in hole-doped samples, whereas it decreases upon electron doping. Increasing temperature substantially enhances μ bare in the hole-doped region, which is naturally explained by the theoretically predicted crossover into a spin-frozen state. Our measurements demonstrate the importance of Hund’s-coupling and electronic correlations, especially for hole-doped BaFe 2 As 2 , as well as the inadequacy of a fully localized or fully itinerant description of the 122 family of Fe pnictides.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Reciprocity between local moments and collective magnetic excitations in the phase diagram of BaFe 2 (As 1-x P x ) 2

Unconventional superconductivity arises at the border between the strong coupling regime with local magnetic moments and the weak coupling regime with itinerant electrons, and stems from the physics of criticality that dissects the two. Unveiling the nature of the quasiparticles close to quantum criticality is fundamental to understand the phase diagram of quantum materials. Here, using resonant inelastic x-ray scattering (RIXS) and Fe-K β emission spectroscopy (XES), we visualize the coexistence and evolution of local magnetic moments and collective spin excitations across the superconducting dome in isovalently-doped BaFe 2 (As 1-x P x ) 2 (0.00 ≤ x ≤0.52). Collective magnetic excitations resolved by RIXS are gradually hardened, whereas XES reveals a strong suppression of the local magnetic moment upon doping. This relationship is captured by an intermediate coupling theory, explicitly accounting for the partially localized and itinerant nature of the electrons in Fe pnictides. Finally, our work identifies a local-itinerant spin fluctuations channel through which the local moments transfer spin excitations to the particle-hole (paramagnons) continuum across the superconducting dome.

36 MATERIALS SCIENCE↗

A uniform metallicity in the outskirts of massive, nearby galaxy clusters

Suzaku measurements of a homogeneous metal distribution of Z ~ 0:3 Solar in the outskirts of the nearby Perseus cluster suggest that chemical elements were deposited and mixed into the intergalactic medium before clusters formed, likely over 10 billion years ago. A key prediction of this early enrichment scenario is that the intracluster medium in all massive clusters should be uniformly enriched to a similar level. Here, we confirm this prediction by determining the iron abundances in the outskirts (r > 0:25r200) of a sample of ten other nearby galaxy clusters observed with Suzaku for which robust measurements based on the Fe-K lines can be made. Across our sample the iron abundances are consistent with a constant value, ZFe = 0:316 ± 0:012 Solar (Χ 2 = 28:85 for 25 degrees of freedom). This is remarkably similar to the measurements for the Perseus cluster of ZFe = 0:314±0:012 Solar, using the Solar abundance scale of Asplund et al. (2009).

79 ASTRONOMY AND ASTROPHYSICS↗

Materials Data on KFe by Materials Project

KFe is delta Molybdenum Boride-like structured and crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. K is bonded in a 3-coordinate geometry to seven equivalent Fe atoms. There are a spread of K–Fe bond distances ranging from 3.53–3.85 Å. Fe is bonded in a 9-coordinate geometry to seven equivalent K and two equivalent Fe atoms. Both Fe–Fe bond lengths are 2.26 Å.

36 MATERIALS SCIENCE↗

Materials Data on K4Fe by Materials Project

K4Fe crystallizes in the tetragonal I4_1/a space group. The structure is zero-dimensional and consists of eight iron molecules and thirty-two potassium molecules.

36 MATERIALS SCIENCE↗