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Alp, Esen E.

Publications and source records attributed to Alp, Esen E..

At least 19 records

57 Fe nuclear resonance vibrational spectroscopic studies of tetranuclear iron clusters bearing terminal iron( III )–oxido/hydroxido moieties

57 Fe nuclear resonance vibrational spectroscopy (NRVS) has been applied to study a series of tetranuclear iron ([Fe 4 ]) clusters based on a multidentate ligand platform (L 3− ) anchored by a 1,3,5-triarylbenzene linker and pyrazolate or (tertbutylamino)pyrazolate ligand (PzNH t Bu − ). These clusters bear a terminal Fe(III)–O/OH moiety at the apical position and three additional iron centers forming the basal positions. The three basal irons are connected with the apical iron center via a μ 4 -oxido ligand. Detailed vibrational analysis via density functional theory calculations revealed that strong NRVS spectral features below 400 cm −1 can be used as an oxidation state marker for the overall [Fe 4 ] cluster core. The terminal Fe(III)–O/OH stretching frequencies, which were observed in the range of 500–700 cm −1 , can be strongly modulated (energy shifts of 20–40 cm −1 were observed) upon redox events at the three remote basal iron centers of the [Fe 4 ] cluster without the change of the terminal Fe(III) oxidation state and its coordination environment. Therefore, the current study provides a quantitative vibrational analysis of how the remote iron centers within the same iron cluster exert exquisite control of the chemical reactivities and thermodynamic properties of the specific iron site that is responsible for small molecule activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Continuous pressure-induced valence and magnetic transitions in EuMnSb 2

EuMnSb 2 is a unique and promising compound with complex magnetism (Eu and Mn sublattices) to realize magnetic control of topological quasiparticles. By applying pressure (P) to this system, we have observed a continuous pressure-induced valence change from Eu 2+ to Eu 3+ . Remarkably, despite the significant valence change in Eu ions, an extremely large increase in the magnetic ordering temperature (T N,Eu ) from 21 K at ambient pressure to 180 K at 28.4 GPa is detected.The substantial enhancement in T N,Eu is likely the consequence of the reduced distance between neighboring Eu ions and the enhanced indirect exchange interaction through increased 4f -5d mixing under pressure. Furthermore, T N,Eu (P) shows a discontinuous change above 8 GPa, although the orthorhombic crystal structure remains stable. Our experimental data indicate the record high value in the magnetic hyperfine field of 151 Eu, reaching 74.1 T at 28.4 GPa and 26 K. In conclusion, these unusual electronic and magnetic transitions revealed by pressure highlight that EuMnSb 2 is a rich magnetic topological semimetal candidate for investigating a multitude of strong correlations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Multicaloric Cryocooling Using Heavy Rare-Earth Free La(Fe,Si) 13 -Based Compounds

The transition toward a carbon-neutral society based on renewable energies goes hand in hand with the availability of energy-efficient technologies. Here, magnetocaloric cooling is a very promising refrigeration technology to fulfill this role regarding cryogenic gas liquefaction. However, the current reliance on highly resource critical, heavy rare-earth-based compounds as magnetocaloric material makes global usage unsustainable. Here, we aim to mitigate this limitation through the utilization of a multicaloric cooling concept, which uses the external stimuli of isotropic pressure and magnetic field to tailor and induce magnetostructural phase transitions associated with large caloric effects. In this study, La 0.7 Ce 0.3 Fe 11.6 Si 1.4 is used as a nontoxic, low-cost, low-criticality multiferroic material to explore the potential, challenges, and peculiarities of multicaloric cryocooling, achieving maximum isothermal entropy changes up to −28 J (kg K) −1 in the temperature range from 190 K down to 30 K. Thus, the multicaloric cooling approach offers an additional degree of freedom to tailor the phase transition properties and may lead to energy-efficient and environmentally friendly gas liquefaction based on designed-for-purpose, noncritical multiferroic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Robust magnetism and crystal structure in Dirac semimetal EuMnBi 2 under high pressure

Dirac materials offer exciting opportunities to explore low-energy carrier dynamics and novel physical phenomena, especially their interaction with magnetism. In this context, this work focuses on studies of pressure control on the magnetic state of EuMnBi 2 , a representative magnetic Dirac semimetal, through time-domain synchrotron Mössbauer spectroscopy in 151 Eu. Contrary to the previous report that the antiferromagnetic order is suppressed by pressure above 4 GPa, we have observed robust magnetic order up to 33.1 GPa. Synchrotron-based x-ray diffraction experiment on a pure EuMnBi 2 sample shows that the tetragonal crystal lattice remains stable up to at least 31.7 GPa.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Strong enhancement of magnetic ordering temperature and structural/valence transitions in EuPd 3 S 4 under high pressure

We present a comprehensive study of the inhomogeneous mixed-valence compound, EuPd 3 S 4 , by electrical transport, X-ray diffraction, time-domain 151 Eu synchrotron Mössbauer spectroscopy, and X-ray absorption spectroscopy measurements under high pressure. Electrical transport measurements show that the antiferromagnetic ordering temperature, T N , increases rapidly from 2.8 K at ambient pressure to 23.5 K at ~19 GPa and plateaus between ~19 and ~29 GPa after which no anomaly associated with T N is detected. A pressure-induced first-order structural transition from cubic to tetragonal is observed, with a rather broad coexistence region (~20 GPa to ~30 GPa) that corresponds to the T N plateau. Mössbauer spectroscopy measurements show a clear valence transition from approximately 50:50 Eu 2+ :Eu 3+ to fully Eu 3+ at ~28 GPa, consistent with the vanishing of the magnetic order at the same pressure. X-ray absorption data show a transition to a fully trivalent state at a similar pressure. Our results show that pressure first greatly enhances T N , most likely via enhanced hybridization between the Eu 4 f states and the conduction band, and then, second, causes a structural phase transition that coincides with the conversion of the europium to a fully trivalent state.

36 MATERIALS SCIENCE↗

The iron oxidation state of Ryugu samples

The Hayabusa2 mission sampled Ryugu, an asteroid that did not suffer extensive thermal metamorphism, and returned rocks to the Earth with no significant air exposure. It therefore offers a unique opportunity to study the redox state of carbonaceous Cb-type asteroids and evaluate the overall redox state of the most primitive rocks of the solar system. An analytical framework was developed to investigate the iron mineralogy and valence state in extraterrestrial material at the micron scale by combining x-ray diffraction, conventional Mössbauer (MS), and nuclear forward scattering (NFS) spectroscopies. An array of standard minerals was analyzed and cross-calibrated between MS and NFS. Then, MS and NFS spectra on three Ryugu grains were collected at the bulk and the micron scales. In Ryugu samples, iron is essentially accommodated in magnetite, clay minerals (serpentine–smectite), and sulfides. Only a single set of Mössbauer parameters was necessary to account for the entire variability observed in MS and NFS spectra, at all spatial scales investigated. These parameters therefore make up a fully consistent iron mineralogical model for the Ryugu samples. As far as MS and NFS spectroscopies are concerned, Ryugu grains are overall similar to each other and share most of their mineralogical features with CI-type chondrites. In detail however, no ferrihydrite is found in Ryugu particles even at the very sensitive scale of Mössbauer spectroscopy. The typical Fe 3+ /Fe tot of clay minerals is much lower than typical redox ratios measured in CI chondrites (Fe 3+ /Fe tot = 85%–90%). Furthermore, magnetite from Ryugu is stoichiometric with no significant maghemite component, whereas up to 12% of maghemite was previously identified in the Orgueil's so-called magnetite. These differences suggest that most CI meteorites suffered terrestrial alteration and that the preterrestrial composition of these carbon-rich samples was less oxidized than previously measured. However, it is not clear yet whether or not the parent bodies of CI chondrites were as reduced as Ryugu. Finally, the high spatial resolution of NFS allows to disentangle the redox state and the crystal chemistry of iron accommodated in serpentine and smectite. The most likely polytype of serpentine is lizardite, containing <35% of Fe 3+ , a fraction of which being tetrahedrally coordinated. Smectite is more oxidized (Fe 3+ /Fe tot > 65%) and mainly contains octahedral ferric iron. In conclusion, this finding implies that these clays formed from highly alkaline fluids and the spatial variability highlighted here may suggest a temporal evolution or a spatial variability of the nature of this fluid.

58 GEOSCIENCES↗

Evolution of magnetism, valence, and crystal lattice in EuCd 2 As 2 under pressure

EuCd 2 As 2 has been proposed to be one of the ideal platforms as an intrinsic topological magnetic system, potentially hosting a single pair of Weyl points when it is tuned into the ferromagnetic state with spins aligned out of plane by either external pressure or chemical doping. To investigate the possible realization of an ideal topological state, we have systematically investigated pressure control of the magnetic state, valence, and crystal structure using synchrotron-based time-domain Mössbauer spectroscopy, x-ray absorption spectroscopy, and powder x-ray diffraction. Our experimental results show that the magnetic configuration remains mostly in plane under pressure up to 42.8 GPa and pressure effectively enhances the magnetic ordering temperature. Meanwhile, Eu ions remain divalent when subjected to pressure up to 35.9 GPa, and the trigonal crystal lattice is maintained up to 34.6 GPa. Our work provides valuable experimental data to benchmark future theoretical studies in magnetic topological materials.

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Isotopic Constraints on the Nature of Primary Precipitates in Archean–Early Paleoproterozoic Iron Formations from Determinations of the Iron Phonon Density of States of Greenalite and 2L- and 6L-Ferrihydrite

Iron formations (IFs) are chemical sedimentary rocks that were widely deposited before the Great Oxidation Event (GOE) around 2.4- 2.2 Ga. It is generally thought that IFs precipitated as hydrated Fe 3+ oxides (HFOs) such as ferrihydrite following surface oxidation of Fe 2+ -rich, anoxic deep waters. This model often implicates biological oxidation and underpins reconstructions of marine nutrient concentrations. However, nanoscale petrography indicates that an Fe 2+ silicate, greenalite, is a common primary mineral in well-preserved IFs, motivating an alternative depositional model of anoxic ferrous silicate precipitation. It is unclear, however, if Fe 2+ -rich silicates can produce the Fe isotopic variations in IFs that are well explained by Fe 2+ oxidation. To address this question, we constrain the equilibrium Fe isotopic ( 56 Fe/ 54 Fe) fractionation of greenalite and ferrihydrite by determining the iron phonon densities of states for those minerals. Here, we use ab initio density functional theory (DFT + U) calculations and nuclear resonant inelastic X-ray scattering spectroscopy to show that ferrous greenalite should be isotopically lighter than ferrihydrite by similar to 1-1.2 parts per thousand at equilibrium, and fractionation should scale linearly with increasing Fe 3+ content in greenalite. By anchoring ferrihydrite-greenalite mineral pair fractionations to published experimental Fe isotopic fractionations between HFOs and aqueous Fe 2+ , we show that ferrous greenalite may produce all but the heaviest pre-GOE Fe isotopic compositions and mixed valence greenalites can produce the entire record. Our results suggest that heavy Fe isotope enrichments alone are not diagnostic of primary IF mineralogies, and ferrihydrite and partially oxidized or even purely ferrous greenalite are all viable primary IF mineralogies.

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Pressure effect on magnetism and valence in ferromagnetic superconductor Eu(Fe 0.75 Ru 0.25 ) 2 As 2

Eu(Fe 0.75 Ru 0.25 ) 2 As 2 is an intriguing system with unusual coexistence of superconductivity and ferromagnetism, providing a unique platform to study the nature of such coexistence. To establish a magnetic phase diagram, time-domain synchrotron Mössbauer experiments in 151 Eu have been performed on a single crystalline Eu(Fe 0.75 Ru 0.25 ) 2 As 2 sample under hydrostatic pressures and at low temperatures. Upon compression the magnetic ordering temperature increases sharply from 20 K at ambient pressure, reaching ~49 K at 10.1GPa. With further compression, the magnetic order is suppressed and eventually collapses. Isomer shift values from Mössbauer measurements and x-ray absorption spectroscopy data at Eu L 3 edge show that pressure drives Eu ions to a homogeneous intermediate valence state with mean valence of ~2.4 at 27.4 GPa, possibly responsible for the suppression of magnetism. Synchrotron powder x-ray diffraction experiment reveals a tetragonal to collapsed-tetragonal structural transition around 5 GPa, a lower transition pressure than in the parent compound. Furthermore, these results provide guidance to further work investigating the interplay of superconductivity and magnetism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Drastic enhancement of magnetic critical temperature and amorphization in topological magnet EuSn 2 P 2 under pressure

High pressure is an effective tool to induce exotic quantum phenomena in magnetic topological insulators by controlling the interplay of magnetic order and topological state. This work presents a comprehensive high-pressure study of the crystal structure and magnetic ground state up to 62 GPa in an intrinsic topological magnet EuSn 2 P 2 . With a combination of high resolution X-ray diffraction, 151 Eu synchrotron Mössbauer spectroscopy, X-ray absorption spectroscopy, molecular orbital calculations, and electronic band structure calculations, it has been revealed that pressure drives EuSn 2 P 2 from a rhombohedral crystal to an amorphous phase at 36 GPa accompanied by a fourfold enhancement of magnetic ordering temperature. In the pressure-induced amorphous phase, Eu ions take an intermediate valence state. The drastic enhancement of magnetic ordering temperature from 30 K at ambient pressure to 130 K at 41.2 GPa resulting from Ruderman–Kittel–Kasuya–Yosida (RKKY) interactions likely attributes to the stronger Eu–Sn interaction at high pressure. These rich results demonstrate that EuSn 2 P 2 is an ideal platform to study the correlation of the enhanced RKKY interactions, disordered lattice, intermediate valence, and topological state.

36 MATERIALS SCIENCE↗

Signature of Many-Body Localization of Phonons in Strongly Disordered Superlattices

Many-body localization (MBL) has attracted significant research attention due to its immunity to thermalization, role in logarithmic entanglement entropy growth, and opportunities to reach exotic quantum orders. However, experimental realization of MBL in solid-state systems has remained challenging. Here we report evidence of a possible phonon MBL phase in disordered GaAs/AlAs superlattices. Through grazing-incidence inelastic X-ray scattering, we observe a strong deviation of the phonon population from equilibrium in disordered samples doped with ErAs nanodots at low temperature, signaling a departure from thermalization. This behavior occurs within finite phonon energy and wavevector windows, suggesting a localization-thermalization crossover. We support our observation by proposing a theoretical model for the effective phonon Hamiltonian in disordered superlattices, and showing that it can be mapped exactly to a disordered 1D Bose-Hubbard model with a known MBL phase. The large on-site repulsion qualitatively explains the experimental findings. Furthermore, our work provides mode-resolved experimental evidence of phonon localization, potentially extending the scope of MBL to disordered solid-state systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Persistent polyamorphism in the chiton tooth: From a new biomineral to inks for additive manufacturing

Engineering structures that bridge between elements with disparate mechanical properties are a significant challenge. Organisms reap synergy by creating complex shapes that are intricately graded. For instance, the wear-resistant cusp of the chiton radula tooth works in concert with progressively softer microarchitectural units as the mollusk grazes on and erodes rock. Herein, we focus on the stylus that connects the ultrahard and stiff tooth head to the flexible radula membrane. Using techniques that are especially suited to probe the rich chemistry of iron at high spatial resolution, in particular synchrotron Mössbauer and X-ray absorption spectroscopy, we find that the upper stylus of Cryptochiton stelleri is in fact a mineralized tissue. Remarkably, the inorganic phase is nano disperse santabarbaraite, an amorphous ferric hydroxyphosphate that has not been observed as a biomineral. The presence of two persistent polyamorphic phases, amorphous ferric phosphate and santabarbaraite, in close proximity, is a unique aspect that demonstrates the level of control over phase transformations in C. stelleri dentition. The stylus is a highly graded material in that its mineral content and mechanical properties vary by a factor of 3 to 8 over distances of a few hundred micrometers, seamlessly bridging between the soft radula and the hard tooth head. Furthermore, the use of amorphous phases that are low in iron and high in water content may be key to increasing the specific strength of the stylus. Finally, we show that we can distill these insights into design criteria for inks for additive manufacturing of highly tunable chitosan-based composites.

36 MATERIALS SCIENCE↗

Iron, magnesium, and titanium isotopic fractionations between garnet, ilmenite, f ayalite, biotite, and tourmaline: Results from NRIXS, ab initio , and study of mineral separates from the Moosilauke metapelite

Interpreting isotopic signatures documented in natural rocks requires knowledge of equilibrium isotopic fractionation factors. Here, we determine equilibrium Fe isotope fractionation factors between several common rock-forming minerals using a comparative approach involving three independent methods: (i) isotopic analyses of natural minerals from a metapelite from Mt. Moosilauke, New Hampshire, for which equilibration temperature and pressure are well constrained to be near the aluminosilicate triple point (T ≃ 500 °C, P ≃ 4 kbar), (ii) Nuclear Resonant Inelastic X-ray Scattering (NRIXS) measurements of Fe force constants of minerals, and (iii) Density Functional Theory (DFT) ab initio calculations of Fe force constants of minerals. The minerals studied for Fe isotopes include, in increasing order of their β-factors: garnet < ilmenite ≈ fayalite < biotite < tourmaline < muscovite ≈ plagioclase. Some of this ordering is affected by the presence of Fe 3+ in the minerals, which tends to form stiffer bonds and be associated with heavy Fe isotope enrichments relative to Fe 2+ . We are, however, able to assess the magnitude of the effect of the ratio Fe 3+ /ΣFe on equilibrium fractionation factors, notably on the ilmenite-hematite solid solution. Equilibrium Fe isotopic fractionation factors between garnet, ilmenite, biotite, tourmaline and fayalite are determined. We also report Mg and Ti isotopic compositions of selected Moosilauke minerals that allow us to better constrain the equilibrium fractionation factors for garnet-biotite-tourmaline (Mg isotopes) and biotite-ilmenite (Ti isotopes). We show how the newly determined equilibrium fractionation factors can be used to address diverse problems in Earth and planetary sciences, notably (i) Fe and Mg isotopic fractionation during anatexis, (ii) Fe isotopic fractionation in lunar ilmenite, and (iii) Ti isotopic fractionation during fluvial transport of minerals.

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Microscopic Phase Diagram of Eu(Fe 1-x Ni x )As 2 ( x = 0,0.04) Under Pressure

This study will go to establish the microscopic P-T phase diagram of recent 112-type iron-pnictides Eu(Fe 1-x Ni x )As- 2 (x = 0,0.04), high-pressure synchrotron Mossbauer spectroscopy experiments in 151 Eu and 57 Fe have been performed. In EuFeAs 2 application of pressure completely suppresses the itinerant electron magnetism from the Fe sublattice and the local-moment magnetism in Eu ions at similar to ~10 and similar to ~11.6 GPa, respectively. High-pressure x-ray diffraction experiments in EuFeAs 2 reveal an anomalous change in the lattice parameters and a discontinuity in volume around 10 GPa, suggesting an isostructural transition at this pressure. With Ni-doping (x = 0.04), a collapse of local magnetic order occurs at similar to ~8GPa, a lower critical pressure compared with the parent compound. In both systems, the suppression of local-moment magnetism is associated with a significant increase of mean valence in Eu ions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The Water-Fe-Pressure dependent single-crystal elastic properties of wadsleyite: Implications for the seismic anisotropy in the upper Mantle Transition Zone

Recent seismic studies suggest an anisotropic Mantle Transition Zone (MTZ) in areas adjacent to subducted slabs. Wadsleyite is the main anisotropy contributor in the upper MTZ, therefore the interpretation of these seismic observations requires the knowledge of single-crystal elastic moduli (C ij s) and the deformation-induced lattice preferred orientation (LPO) of wadsleyite. Wadsleyite can host up to 3 wt% water in its crystal structure as point defects in the form of hydroxyl groups, however, the combined effect of water content, Fe content, and pressure on the C ij s of wadsleyite remains unclear. In this study, we measured the high-pressure single-crystal elasticity of a synthetic hydrous Fe-bearing wadsleyite (0.14(5) wt% water, Fe#=9.4, Fe 3+ /ΣFe=0.3) up to 18.2 (2) GPa. In combination with previous experimental data, we separated the effects of pressure, water, and Fe contents on the Cijs and intrinsic elastic anisotropy of wadsleyite. Overall, our results suggest that the intrinsic elastic anisotropy of wadsleyite decreases with pressure, water, and Fe contents. At 15 GPa, increasing the water content by 0.1 wt% or Fe# by 1 decreases the V P and V S anisotropy of wadsleyite by ~1.1-1.3%, and ~0.8-1.3% in average, respectively. Combined with the LPO determined in previous deformation experiments, we modeled the seismic anisotropy in the upper MTZ generated by a sub-vertical mantle flow near cold subducted slabs and a sub-horizontal mantle flow in the ambient mantle. In both scenarios, the LPO of wadsleyite leads to V SV (vertically polarized shear wave velocity) > V SH (horizontally polarized shear wave velocity). Our results suggest that wadsleyite may account for a weak anisotropic MTZ (<1%) on the global scale. Considering the fact that water decreases the elastic anisotropy but promotes LPO of wadsleyite, seismic anisotropy may not be a good water sensor.

36 MATERIALS SCIENCE↗

Loss and Isotopic Fractionation of Alkali Elements during Diffusion-Limited Evaporation from Molten Silicate: Theory and Experiments

Moderately volatile elements (MVEs) are variably depleted in planetary bodies, reflecting the imprints of nebular and planetary processes. Among MVEs, Na, K, and Rb are excellent tracers for unraveling the history of MVE depletion in planetary bodies because they have similar geochemical behaviors but can be chemically fractionated by evaporation and condensation processes. Furthermore, K and Rb are amenable to high-precision isotopic analyses, which can help constrain the conditions of evaporation and condensation. To quantitatively understand why Na, K, and Rb are depleted in planetary bodies, we have carried out vacuum evaporation experiments from basaltic melt at 1200 and 1400 °C to study their evaporation kinetics and isotopic fractionations. We chose this composition because it is relevant to evaporation from small differentiated planetesimals. The Rb isotopic compositions of the evaporation residues were measured by multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), and the K isotopic compositions were measured along profiles across the residues by secondary ion mass spectrometry (SIMS). In the 1400 °C run products, we found that the concentrations of both K and Rb in the run products decreased from core to rim, which was accompanied by a heavy K isotope enrichment near the surface. This indicates that, in this run, evaporation was limited by diffusion. To use those data quantitatively, we derive analytical equations that describe the evaporation rate and isotopic fractionation associated with diffusion-limited evaporation from a sphere, slab, and cylinder in transient and quasi-steady state regimes. This model is used to tease out the roles that diffusive transport in the melt and evaporation at the melt/gas interface play in setting the elemental depletion and isotopic composition of the residue. Under our experimental conditions, volatility decreases in the order of Na, Rb, and K. Using our experimental results in a thermodynamic model, we have estimated the product γΓ of activity coefficients × evaporation coefficients of Na, Rb, and K. The measured isotopic compositions of the residues are well explained using Rayleigh distillations, whereby the relative volatilities of K and Rb isotopes are given by the square root of their masses. We use our results and previously published data to predict how K and Rb could have been lost as a function of temperature, melt composition, oxygen fugacity, and saturation degree relevant to Vesta’s building blocks. We find that the K and Rb depletions, K/Rb elemental fractionation, and δ 41 K and δ 87 Rb isotopic fractionations of Vesta (as sampled by howardite-eucrite-diogenite (HED) meteorites) are best explained by evaporation of submillimeter size objects for 0.1-10 years at moderate temperatures (~1050 °C) in a medium ~98.8% saturated.

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