Bronze Age weight systems as a measure of market integration in Western Eurasia.

Weighing technology was invented around 3000 BCE between Mesopotamia and Egypt and became widely adopted in Western Eurasia within ∼2,000 y. For the first time in history, merchants could rely on an objective frame of reference to quantify economic value. The subsequent emergence of different weight systems goes hand in hand with the formation of a continental market. However, we still do not know how the technological transmission happened and why different weight systems emerged along the way. Here, we show that the diffusion of weighing technology can be explained as the result of merchants' interaction and the emergence of primary weight systems as the outcome of the random propagation of error constrained by market self-regulation. We found that the statistical errors of early units between Mesopotamia and Europe overlap significantly. Our experiment with replica weights gives error figures that are consistent with the archaeological sample. We used these figures to develop a model simulating the formation of primary weight systems based on the random propagation of error over time from a single original unit. The simulation is consistent with the observed distribution of weight units. We demonstrate that the creation of the earliest weight systems is not consistent with a substantial intervention of political authorities. Our results urge a revaluation of the role of individual commercial initiatives in the formation of the first integrated market in Western Eurasia.

Magnetically Induced Binary Ferrocene with Oxidized Iron.

Ferrocene is perhaps the most popular and well-studied organometallic molecule, but our understanding of its structure and electronic properties has not changed for more than 70 years. In particular, all previous attempts of chemically oxidizing pure ferrocene by binding directly to the iron center have been unsuccessful, and no significant change in structure or magnetism has been reported. Using a metal organic framework host material, we were able to fundamentally change the electronic and magnetic structure of ferrocene to take on a never-before observed physically stretched/bent high-spin Fe(II) state, which readily accepts O2 from air, chemically oxidizing the iron from Fe(II) to Fe(III). We also show that the binding of oxygen is reversible through temperature swing experiments. Our analysis is based on combining Mößbauer spectroscopy, extended X-ray absorption fine structure, in situ infrared, SQUID, thermal gravimetric analysis, and energy dispersive X-ray fluorescence spectroscopy measurements with ab initio modeling.

Direct Mechanochemical Synthesis, Phase Stability, and Electrochemical Performance of α-NaFeO2.

To better understand polymorph control in transition metal oxides, the mechanochemical synthesis of NaFeO2 was explored. Herein, we report the direct synthesis of α-NaFeO2 through a mechanochemical process. By milling Na2O2 and γ-Fe2O3 for 5 h, α-NaFeO2 was prepared without high-temperature annealing needed in other synthesis methods. While investigating the mechanochemical synthesis, it was observed that changing the starting precursors and mass of precursors affects the resulting NaFeO2 structure. Density functional theory calculations on the phase stability of NaFeO2 phases show that the α phase is stabilized over the ß phase in oxidizing environments, which is provided by the oxygen-rich reaction between Na2O2 and Fe2O3. This provides a possible route to understanding polymorph control in NaFeO2. Annealing the as-milled α-NaFeO2 at 700 °C has resulted in increased crystallinity and structural changes that improved electrochemical performance in terms of capacity over the as-milled sample.

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.

Charge Density Wave in Kagome Lattice Intermetallic ScV_{6}Sn_{6}.

Materials hosting kagome lattices have drawn interest for the diverse magnetic and electronic states generated by geometric frustration. In the AV_{3}Sb_{5} compounds (A=K, Rb, Cs), stacked vanadium kagome layers give rise to unusual charge density waves (CDW) and superconductivity. Here we report single-crystal growth and characterization of ScV_{6}Sn_{6}, a hexagonal HfFe_{6}Ge_{6}-type compound that shares this structural motif. We identify a first-order phase transition at 92 K. Single crystal x-ray and neutron diffraction reveal a charge density wave modulation of the atomic lattice below this temperature. This is a distinctly different structural mode than that observed in the AV_{3}Sb_{5} compounds, but both modes have been anticipated in kagome metals. The diverse HfFe_{6}Ge_{6} family offers more opportunities to tune ScV_{6}Sn_{6} and explore density wave order in kagome lattice materials.

RUScal: Software for the analysis of resonant ultrasound spectroscopy measurements.

Resonant ultrasound spectroscopy is used to nondestructively measure the elastic resonances of small solids to elucidate the material's elastic properties or other qualities like size, shape, or composition. Here, we introduce the software RUScal for the purpose of determining elastic properties by analyzing the eigenfrequencies of solid specimens with common shapes, such as rectangular parallelepipeds, cylinders (solid and hollow tube), ellipsoids, and octahedrons, as well as irregularly shaped ellipsoids that can be described analytically. All symmetry classes are supported, from isotropic to triclinic, along with the option to add or remove up to three orthogonal mirror planes as well as the ability to reorient the crystal axes with respect the sample edges via Euler angles. Additional features include tools to help find initial sets of elastic constants, including grid exploration and Monte Carlo methods, a tool to analyze frequencies as a function of sample length or crystal orientation, an error analysis tool to assess fit quality, and formatting of the input and output files for batch fitting, e.g., as a function of temperature. This software was validated with published resonant ultrasound spectroscopy data for various materials, shapes, and symmetries with noted improvements in calculation time compared to finite element methods.

Deconvoluting the Magnetic Structure of the Commensurately Modulated Quinary Zintl Phase Eu11-xSrxZn4Sn2As12.

The structure, magnetic properties, and 151Eu and 119Sn Mössbauer spectra of the solid-solution Eu11-xSrxZn4Sn2As12 are presented. A new commensurately modulated structure is described for Eu11Zn4Sn2As12 (R3m space group, average structure) that closely resembles the original structural description in the monoclinic C2/c space group with layers of Eu, puckered hexagonal Zn2As3 sheets, and Zn2As6 ethane-like isolated pillars. The solid-solution Eu11-xSrxZn4Sn2As12 (0 < x < 10) is found to crystallize in the commensurately modulated R3 space group, related to the parent phase but lacking the mirror symmetry. Eu11Zn4Sn2As12 orders with a saturation plateau at 1 T for 7 of the 11 Eu2+ cations ferromagnetically coupled (5 K) and shows colossal magnetoresistance at 15 K. The magnetic properties of Eu11Zn4Sn2As12 are investigated at higher fields, and the ferromagnetic saturation of all 11 Eu2+ cations occurs at ∼8 T. The temperature-dependent magnetic properties of the solid solution were investigated, and a nontrivial structure-magnetization correlation is revealed. The temperature-dependent 151Eu and 119Sn Mössbauer spectra confirm that the europium atoms in the structure are all Eu2+ and that the tin is consistent with an oxidation state of less than four in the intermetallic region. The spectral areas of both Eu(II) and Sn increase at the magnetic transition, indicating a magnetoelastic effect upon magnetic ordering.

Phonon Spectroscopy in Antimony and Tellurium Oxides.

α-Sb2O3 (senarmontite), ß-Sb2O3 (valentinite), and α-TeO2 (paratellurite) are compounds with pronounced stereochemically active Sb and Te lone pairs. The vibrational and lattice properties of each have been previously studied but often lead to incomplete or unreliable results due to modes being inactive in infrared or Raman spectroscopy. Here, we present a study of the relationship between bonding and lattice dynamics of these compounds. Mössbauer spectroscopy is used to study the structure of Sb in α-Sb2O3 and ß-Sb2O3, whereas the vibrational modes of Sb and Te for each oxide are investigated using nuclear inelastic scattering, and further information on O vibrational modes is obtained using inelastic neutron scattering. Additionally, vibrational frequencies obtained by density functional theory (DFT) calculations are compared with experimental results in order to assess the validity of the utilized functional. Good agreement was found between DFT-calculated and experimental density of phonon states with a 7% scaling factor. The Sb-O-Sb wagging mode of α-Sb2O3 whose frequency was not clear in most previous studies is experimentally observed for the first time at ∼340 cm-1. Softer lattice vibrational modes occur in orthorhombic ß-Sb2O3 compared to cubic α-Sb2O3, indicating that the antimony bonds are weakened upon transforming from the molecular α phase to the layer-chained ß structure. The resulting vibrational entropy increase of 0.45 ± 0.1 kB/Sb2O3 at 880 K accounts for about half of the α-ß transition entropy. The comparison of experimental and theoretical approaches presented here provides a detailed picture of the lattice dynamics in these oxides beyond the zone center and shows that the accuracy of DFT is sufficient for future calculations of similar material structures.

High-pressure nuclear inelastic scattering with backscattering monochromatization.

The capability to perform high-pressure low-temperature nuclear inelastic scattering on 125Te and 121Sb with a sapphire backscattering monochromator is presented. This technique was applied to measure nuclear inelastic scattering in TeO2 at pressures up to 10 GPa and temperatures down to 25 K. The evaluated partial Te densities of phonon states were compared with theoretical calculations and with Raman scattering measured under the same conditions. The high-pressure cell developed in this work can also be used for other techniques at pressures up to at least 100 GPa.

Structural, Chemical, Electrical, and Thermal Properties of n-Type NbFeSb.

We report on the structural, chemical, electrical, and thermal properties of n-type polycrystalline NbFeSb synthesized by induction melting of the elements. Although several studies on p-type conduction of this half-Heusler composition have recently been reported, including reports of relatively high thermoelectric properties, very little has been reported on the transport properties of  n-type compositions. We combine transport property investigations together with short- and long-range structural data obtained by Mössbauer spectroscopy of iron-57 and antimony-121 and by neutron total scattering, as well as first-principles calculations. In our investigation, we show that n-type conduction can occur from antiphase boundaries in this material. This work is intended to provide a greater understanding of the fundamental properties of NbFeSb as this material continues to be of interest for potential thermoelectric applications.

Structure Characterization and Properties of K-Containing Copper Hexacyanoferrate.

Copper hexacyanoferrate, Cu(II)[Fe(III)(CN)6]2/3·nH2O, was synthesized, and varied amounts of K(+) ions were inserted via reduction by K2S2O3 (aq). Ideally, the reaction can be written as Cu(II)[Fe(III)(CN)6]2/3·nH2O + 2x/3K(+) + 2x/3e(-) ↔ K2x/3Cu(II)[Fe(II)xFe(III)1-x(CN)6]2/3·nH2O. Infrared, Raman, and Mössbauer spectroscopy studies show that Fe(III) is continuously reduced to Fe(II) with increasing x, accompanied by a decrease of the a-axis of the cubic Fm3̅m unit cell. Elemental analysis of K by inductively coupled plasma shows that the insertion only begins when a significant fraction, ∼20% of the Fe(III), has already been reduced. Thermogravimetric analysis shows a fast exchange of water with ambient atmosphere and a total weight loss of ∼26 wt % upon heating to 180 °C, above which the structure starts to decompose. The crystal structures of Cu(II)[Fe(III)(CN)6]2/3·nH2O and K2/3Cu[Fe(CN)6]2/3·nH2O were refined using synchrotron X-ray powder diffraction data. In both, one-third of the Fe(CN)6 groups are vacant, and the octahedron around Cu(II) is completed by water molecules. In the two structures, difference Fourier maps reveal three additional zeolitic water sites (8c, 32f, and 48g) in the center of the cavities formed by the -Cu-N-C-Fe- framework. The K-containing compound shows an increased electron density at two of these sites (32f and 48g), indicating them to be the preferred positions for the K(+) ions.

Transition-Metal Carbodiimides as Molecular Negative Electrode Materials for Lithium- and Sodium-Ion Batteries with Excellent Cycling Properties.

We report evidence for the electrochemical activity of transition-metal carbodiimides versus lithium and sodium. In particular, iron carbodiimide, FeNCN, can be efficiently used as negative electrode material for alkali-metal-ion batteries, similar to its oxide analogue FeO. Based on (57)Fe Mössbauer and infrared spectroscopy (IR) data, the electrochemical reaction mechanism can be explained by the reversible transformation of the Fe-NCN into Li/Na-NCN bonds during discharge and charge. These new electrode materials exhibit higher capacity compared to well-established negative electrode references such as graphite or hard carbon. Contrary to its oxide analogue, iron carbodiimide does not require heavy treatments (such as nanoscale tailoring, sophisticated textures, or coating) to obtain long cycle life with current density as high as 9 A g(-1) for hundreds of charge-discharge cycles. Similar to the iron compound, several other transition-metal carbodiimides M(x)(NCN)y with M=Mn, Cr, Zn can cycle successfully versus lithium and sodium. Their electrochemical activity and performance open the way to the design of a novel family of anode materials.

Eu9Cd4-xCM2+x-y□ySb9: Ca9Mn4Bi9-type structure stuffed with coinage metals (Cu, Ag, and Au) and the challenges with classical valence theory in describing these possible zintl phases.

The synthesis, crystal structure, magnetic properties, and europium Mössbauer spectroscopy of the new members of the 9-4-9 Zintl family of Eu(9)Cd(4-x)CM(2+x-y)□(y)Sb(9) (CM = coinage metal: Au, Ag, and Cu) are reported. These compounds crystallize in the Ca(9)Mn(4)Bi(9) structure type (9-4-9) with the 4g interstitial site almost half-occupied by coinage metals; these are the first members in the 9-4-9 family where the interstitial positions are occupied by a monovalent metal. All previously known compounds with this structure type include divalent interstitials where these interstitials are typically the same as the transition metals in the anionic framework. Single-crystal magnetic susceptibility data indicate paramagnetic behavior for all three compounds with antiferromagnetic ordering below 10 K (at 100 Oe) that shifts to lower temperature (<7 K) by applying a 3 T magnetic field. (151)Eu Mössbauer spectra were collected on polycrystalline powder samples of Eu(9)Cd(4-x)CM(2+x-y)□(y)Sb(9) at 50 and 6.5 K in order to evaluate the valence of Eu cations. Although the Zintl formalism states that the five crystallographically distinct Eu sites in Eu(9)Cd(4-x)CM(2+x-y)□(y)Sb9 should bear Eu(2+), the Mössbauer spectral isomer shifts are clearly indicative of both 2+ and 3+ valence of the Eu cations with the Cu- and Au-containing compounds showing higher amounts of Eu(3+). This electronic configuration leads to an excess of negative charge in these compounds that contradicts the expected valence-precise requirement of Zintl phases. The spectra obtained at 6.5 K reveal magnetic ordering for both Eu(2+) and Eu(3+). The field dependence of Eu(2+) indicates two distinct magnetic sublattices, with higher and lower fields, and of a small field for Eu(3+). The site symmetry of the five Eu sites is not distinguishable from the Mössbauer data.

On the True Indium Content of In-Filled Skutterudites.

The incongruently melting single-filled skutterudite InxCo4Sb12 is known as a promising bulk thermoelectric material. However, the products of current bulk syntheses contain always impurities of InSb, Sb, CoSb, or CoSb2, which prevent an unbiased determination of its thermoelectric properties. We report a new two-step synthesis of high-purity InxCo4Sb12 with nominal compositions x = 0.12, 0.15, 0.18, and 0.20 that separates the kieftite (CoSb3) formation from the topotactic filler insertion. This approach allows conducting the reactions at lower temperatures with shorter reaction times and circumventing the formation of impurity phases. The synthesis can be extended to other filled skutterudites. High-density (>98%) pellets for thermoelectric characterization were prepared by current-assisted short-time sintering. Sample homogeneity was demonstrated by potential and Seebeck microprobe measurements of the complete pellet surfaces. Synchrotron X-ray diffraction showed a purity of 99.9% product with traces (≤0.1%) of InSb in samples of nominal composition In0.18Co4Sb12 and In0.20Co4Sb12. Rietveld refinements revealed a linear correlation between the true In occupancy and the lattice parameter a. This allows the determination of the true In filling in skutterudites and predicting the In content of unknown AxCo4Sb12. The high purity of InxCo4Sb12 allowed studying the transport properties without bias from side phases. A figure of merit close to unity at 420 °C was obtained for a sample of a true composition of In0.160(2)Co4Sb12 (nominal composition In0.18Co4Sb12). The lower degree of In filling has a dramatic effect on the thermoelectric properties as demonstrated by the sample of nominal composition In0.20Co4Sb12. The presence of InSb in amounts of ∼0.1 vol% led to a substantially lower degree of interstitial site filling of 0.144, and the figure of merit zT decreased by 18%, which demonstrates the significance of the true filler atom content in skutterudite materials.

Nanocrystalline silicon: lattice dynamics and enhanced thermoelectric properties.

Silicon has several advantages when compared to other thermoelectric materials, but until recently it was not used for thermoelectric applications due to its high thermal conductivity, 156 W K(-1) m(-1) at room temperature. Nanostructuration as means to decrease thermal transport through enhanced phonon scattering has been a subject of many studies. In this work we have evaluated the effects of nanostructuration on the lattice dynamics of bulk nanocrystalline doped silicon. The samples were prepared by gas phase synthesis, followed by current and pressure assisted sintering. The heat capacity, density of phonons states, and elastic constants were measured, which all reveal a significant, ≈25%, reduction in the speed of sound. The samples present a significantly decreased lattice thermal conductivity, ≈25 W K(-1) m(-1), which, combined with a very high carrier mobility, results in a dimensionless figure of merit with a competitive value that peaks at ZT≈ 0.57 at 973 °C. Due to its easily scalable and extremely low-cost production process, nanocrystalline Si prepared by gas phase synthesis followed by sintering could become the material of choice for high temperature thermoelectric generators.

Giant Modulation of Refractive Index from Picoscale Atomic Displacements.

It is shown that structural disorder-in the form of anisotropic, picoscale atomic displacements-modulates the refractive index tensor and results in the giant optical anisotropy observed in BaTiS3, a quasi-1D hexagonal chalcogenide. Single-crystal X-ray diffraction studies reveal the presence of antipolar displacements of Ti atoms within adjacent TiS6 chains along the c-axis, and threefold degenerate Ti displacements in the a-b plane. 47/49Ti solid-state NMR provides additional evidence for those Ti displacements in the form of a three-horned NMR lineshape resulting from a low symmetry local environment around Ti atoms. Scanning transmission electron microscopy is used to directly observe the globally disordered Ti a-b plane displacements and find them to be ordered locally over a few unit cells. First-principles calculations show that the Ti a-b plane displacements selectively reduce the refractive index along the ab-plane, while having minimal impact on the refractive index along the chain direction, thus resulting in a giant enhancement in the optical anisotropy. By showing a strong connection between structural disorder with picoscale displacements and the optical response in BaTiS3, this study opens a pathway for designing optical materials with high refractive index and functionalities such as large optical anisotropy and nonlinearity.

(Mg,Mn,Fe,Co,Ni)O: A rocksalt high-entropy oxide containing divalent Mn and Fe.

High-entropy oxides (HEOs) have aroused growing interest due to fundamental questions relating to their structure formation, phase stability, and the interplay between configurational disorder and physical and chemical properties. Introducing Fe(II) and Mn(II) into a rocksalt HEO is considered challenging, as theoretical analysis suggests that they are unstable in this structure under ambient conditions. Here, we develop a bottom-up method for synthesizing Mn- and Fe-containing rocksalt HEO (FeO-HEO). We present a comprehensive investigation of its crystal structure and the random cation-site occupancy. We show the improved structural robustness of this FeO-HEO and verify the viability of an oxygen sublattice as a buffer layer. Compositional analysis reveals the valence and spin state of the iron species. We further report the antiferromagnetic order of this FeO-HEO below the transition temperature ~218 K and predict the conditions of phase stability of Mn- and Fe-containing HEOs. Our results provide fresh insights into the design and property tailoring of emerging classes of HEOs.

Paramagnetic nanoparticles as potential MRI contrast agents: characterization, NMR relaxation, simulations and theory.

OBJECT: Paramagnetic nanoparticles, mainly rare earth oxides and hydroxides, have been produced these last few years for use as MRI contrast agents. They could become an interesting alternative to iron oxide particles. However, their relaxation properties are not well understood. MATERIALS AND METHODS: Magnetometry, (1)H and (2)H NMR relaxation results at different magnetic fields and electron paramagnetic resonance are used to investigate the relaxation induced by paramagnetic particles. When combined with computer simulations of transverse relaxation, they allow an accurate description of the relaxation induced by paramagnetic particles. RESULTS: For gadolinium hydroxide particles, both T(1) and T(2) relaxation are due to a chemical exchange of protons between the particle surface and bulk water, called inner sphere relaxation. The inner sphere is also responsible for T(1) relaxation of dysprosium, holmium, terbium and erbium containing particles. However, for these latter compounds, T(2) relaxation is caused by water diffusion in the field inhomogeneities created by the magnetic particle, the outer-sphere relaxation mechanism. The different relaxation behaviors are caused by different electron relaxation times (estimated by electron paramagnetic resonance). CONCLUSION: These findings may allow tailoring paramagnetic particles: ultrasmall gadolinium oxide and hydroxide particles for T(1) contrast agents, with shapes ensuring the highest surface-to-volume ratio. All the other compounds present interesting T(2) relaxation performance at high fields. These results are in agreement with computer simulations and theoretical predictions of the outer-sphere and static dephasing regime theories. The T(2) efficiency would be optimum for spherical particles of 40-50 nm radius.

Shape induced symmetry in self-assembled mesocrystals of iron oxide nanocubes.

Grazing incidence small-angle scattering and electron microscopy have been used to show for the first time that nonspherical nanoparticles can assemble into highly ordered body-centered tetragonal mesocrystals. Energy models accounting for the directionality and magnitude of the van der Waals and dipolar interactions as a function of the degree of truncation of the nanocubes illustrated the importance of the directional dipolar forces for the formation of the initial nanocube clusters and the dominance of the van der Waals multibody interactions in the dense packed arrays.

Shape-induced superstructure formation in concentrated ferrofluids under applied magnetic fields.

The field-induced ordering of concentrated ferrofluids based on spherical and cuboidal maghemite nanoparticles is studied using small-angle neutron scattering, revealing a qualitative effect of the faceted shape on the interparticle interactions as shown in the structure factor and correlation lengths. Whereas a spatially disordered hard-sphere interaction potential with a short correlation length is found for ∼9 nm spherical nanoparticles, nanocubes of a comparable particle size exhibit a more pronounced interparticle interaction and the formation of linear arrangements. Analysis of the anisotropic two-dimensional pair distance correlation function gives insight into the real-space arrangement of the nanoparticles. On the basis of the short interparticle distances found here, oriented attachment, i.e. a face-to-face arrangement of the nanocubes, is likely. The unusual field dependence of the interparticle correlations suggests a field-induced structural rearrangement.