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At least 19 records

Theoretical and experimental studies of compression and shear deformation behavior of Osmium to 280 GPa

Abstract The compression behavior of osmium metal was investigated up to 280 GPa (volume compression V/V o = 0.725) under nonhydrostatic conditions at ambient temperature using angle dispersive axial x-ray diffraction (A-XRD) with a diamond anvil cell (DAC). In addition, shear strength of osmium was measured to 170 GPa using radial x-ray diffraction (R-XRD) technique in DAC. Both diffraction techniques in DAC employed platinum as an internal pressure standard. Density functional theory (DFT) calculations were also performed, and the computed lattice parameters and volumes under compression are in good agreement with the experiments. DFT predicts a monotonous increase in axial ratio ( c/a ) with pressure and the structural anomalies of less than 1% in ( c/a ) ratio reported below 150 GPa were not reproduced in theoretical calculations and hydrostatic measurements. The measured value of shear strength of osmium ( τ ) approaches a limiting value of 6 GPa above a pressure of 50 GPa in contrast to theoretical predictions of 24 GPa and is likely due to imperfections in polycrystalline samples. DFT calculations also enable the studies of shear and tensile deformations. The theoretical ideal shear stress is found along the (001)[1–10] shear direction with the maximal shear stress ∼24 GPa at critical strain ∼0.13.

Lin, Chia-Min↗

High-pressure structural parameters and equation of state of osmium to 207 GPa

We studied the most incompressible transition metal osmium (Os) under high pressure. There is significant interest in Os because of the structural anomalies attributed to topological transitions in the Fermi surface for valence electrons in the hexagonal close-packed phase. We report on measurements of structural parameters and equation of state on Os metal to a pressure of 207 GPa at ambient temperature using platinum as a pressure standard. We also obtained angle-dispersive X-ray diffraction data at a synchrotron source with closely spaced pressure intervals to observe any discontinuities or anomalies in the axial c/a ratio at high pressures. Rietveld refinements of X-ray diffraction data show a slowly varying axial ratio (c/a) with a broad minimum at 75 GPa. Our data do not provide any evidence of anomalous behavior in the c/a ratio in Os at 25 or 150 GPa as have been reported in previous studies. These experimental results are in agreement with theoretical calculations that do not predict any anomalous behavior in c/a ratio in Os under extreme conditions. We present an equation of state for Os to 207 GPa (V/V 0 = 0.761) at ambient temperature and compare our results with the previously published data.

36 MATERIALS SCIENCE↗

Short review of high-pressure crystal growth and magnetic and electrical properties of solid-state osmium oxides

High-pressure crystal growth and synthesis of selected solid-state osmium oxides, many of which are perovskite-related types, are briefly reviewed, and their magnetic and electrical properties are introduced. Crystals of the osmium oxides, including NaOsO{sub 3}, LiOsO{sub 3}, and Na{sub 2}OsO{sub 4}, were successfully grown under high-pressure and high-temperature conditions at 6 GPa in the presence of an appropriate amount of flux in a belt-type apparatus. The unexpected discovery of a magnetic metal–insulator transition in NaOsO{sub 3}, a ferroelectric-like transition in LiOsO{sub 3}, and high-temperature ferrimagnetism driven by a local structural distortion in Ca{sub 2}FeOsO{sub 6} may represent unique features of the osmium oxides. The high-pressure and high-temperature synthesis and crystal growth has played a central role in the development of solid-state osmium oxides and the elucidation of their magnetic and electronic properties toward possible use in multifunctional devices. - Graphical Abstract: Flux-grown crystals of NaOsO{sub 3} under high-pressure and high-temperature conditions in a belt-type apparatus. The crystal shows a magnetically driven metal–insulator transition at a temperature of 410 K. - Highlights: • Short review of high-pressure crystal growth of solid-state osmium oxides. • Wide variety of magnetic properties of solid-state osmium oxides. • Perovskite and related dense structures stabilized at 3–17 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-Site Osmium Catalysts on MgO: Reactivity and Catalysis of CO Oxidation

MgO-supported osmium dioxo species, described as Os(=O) 2 {-Osupport} 1 or 2 (the brackets denote O atoms of the MgO surface), formed from Os 3 (CO) 12 via supported Os(CO) 2 , and characterized by spectroscopy, microscopy, and theory, react with ethylene at 298 K to form osmium glycol species or with CO to give osmium mono- and di-carbonyls. Os(=O) 2 {-Osupport} 1 or 2 is the precursor of a CO oxidation catalyst characterized by a turnover frequency of 4.0×10 -3 (molecules of CO)/(Os atom×s) at 473 K; the active species are inferred to be osmium monocarbonyls. The structures and frequencies calculated at the level of density functional theory with the B3LYP functional bolster the experimental results and facilitate structural assignments. The lowest-energy structures have various osmium oxidation and spin states. The results demonstrate not only new chemistry of the supported single-site catalysts but also their complexity and the value of complementary techniques used in concert to unravel the chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Osmium coated diffraction grating in the Space Shuttle environment - Performance

Samples coated with osmium were flown on the early Shuttle test flights, and on the return of these samples, the osmium coating was found to have disappeared, evidently due to the oxidation of the material in the atomic oxygen atmosphere. An instrument flown on the Spacelab 1 mission comprised an array of five spectrometers covering the extreme ultraviolet (EUV) to near-IR wavelengths. The EUV spectrometer contained an osmium-coated reflective grating located fairly deep within the instruments. Here, results of an assessment of the reflectivity and stability of the osmium surface over the course of the ten-day mission are reported. It is concluded that the osmium reflective coating remained stable relative to the spectrometer coated with MgF2 over the course of the mission. In addition, the ratio of sensitivity of these two spectrometers did not change in any major way from the time of the laboratory calibration until the time of flight two years later. Any changes are within the 50-percent calibration uncertainty.

Torr, M. R.↗

Unexpected Hole Doping of Graphene by Osmium Adatoms

Abstract The electronic transport of monolayer graphene devices is studied before and after in situ deposition of a sub‐monolayer coating of osmium adatoms. Unexpectedly, and unlike all other metallic adatoms studied to date, osmium adatoms shift the charge neutrality point to more positive gate voltages. This indicates that osmium adatoms act as electron acceptors and thus leave the graphene hole‐doped. Analysis of transport data suggest that Os adatoms behave as charged impurity scatterers, albeit with a surprisingly low charge‐doping efficiency. The charge neutrality point of graphene is found to vary non‐monotonically with gate voltage as the sample is warmed to room temperature, suggesting that osmium diffuses on the surface but is not completely removed.

Elias, Jamie A.↗

η 2 -SO 2 Linkage Photoisomer of an Osmium Coordination Complex

We report the discovery of an n 2 -SO 2 linkage photoisomer in the osmium pentaammine coordination complex, [Os(NH 3 ) 5 (SO 2 )][Os(NH 3 ) 5 (SO 3 )]Cl 4 (1). Its dark and light-induced crystal structures are determined via synchrotron X-ray crystallography, at 100K, where the photo-induced state is metastable in a single crystal that has been stimulated by 505 nm light for 2.5 hrs. The SO 2 photoisomer in the [Os(NH 3 ) 5 (SO 2 )] 2+ cation contrasts starkly with the photo-inactivity of the SO 3 ligand in its companion [Os(NH 3 ) 5 (SO 3 )] 2+ cation within the crystallographic asymmetric unit of this single crystal. Panchromatic optical absorption characteristics of this single crystal are revealed in both dark and light-induced states, using concerted absorption spectroscopy and optical microscopy. Its optical absorption halves across most of its visible spectrum, upon exposure to 505nm light. The SO 2 ligand seems to be responsible for this photo-induced bleaching effect, judging from a comparison of the dark and light-induced crystal structures of 1. The SO 2 linkage photo-isomerism is found to be thermally reversible and so this complex presents a rare example of an osmium-based solid-state optical switch. Such switching in an osmium-based complex is significant be-cause bottom-row transition metals stand to offer linkage photo-isomerism with the greatest photo-conversion levels and thermal stability. Furthermore, the demonstration of n 2 -SO 2 bonding in this complex also represents a fundamental contribution to osmium coordination chemistry

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rhenium-osmium-isotope constraints on the age of iron meteorites

Rhenium and osmium concentrations and the osmium isotopic compositions of iron meteorites were determined by negative thermal ionization mass spectrometry. Data for the IIA iron meteorites define an isochron with an uncertainty of approximately +/-31 million years for meteorites about 4500 million years old. Although an absolute rhenium-osmium closure age for this iron group cannot be as precisely constrained because of uncertainty in the decay constant of Re-187, an age of 4460 million years ago is the minimum permitted by combined uncertainties. These age constraints imply that the parent body of the IIAB magmatic irons melted and subsequently cooled within 100 million years after the formation of the oldest portions of chondrites. Other iron meteorites plot above the IIA isochron, indicating that the planetary bodies represented by these iron groups may have cooled significantly later than the parent body of the IIA irons.

Horan, M. F.↗

Analysis of the spectrum of the (5d{sup 6}+5d{sup 5}6s)−(5d{sup 5}6p+5d{sup 4}6s6p) transitions of two times ionized osmium (Os III)

The spectrum of osmium was observed in the (225–2100) Å wavelength region. The (5d{sup 6} + 5d{sup 5}6s)− (5d{sup 5}6p + 5d{sup 4}6s6p) transition array of two times ionized osmium, Os III, has been investigated and 1039 spectral lines have been classified in the region. The analysis has led to the determination of the 5d{sup 6}, 5d{sup 5}6s, 5d{sup 5}6p and 5d{sup 4}6s6p configurations. Fifty-eight levels of the 5d{sup 6} and 5d{sup 5}6s configurations in the even system and 142 levels of the 5d{sup 5}6p and 5d{sup 4}6s6p configurations in the odd system have been established. The orthogonal operators technique was used to calculate the level structure and transition probabilities. The energy parameters have been determined by the least squares fit to the observed levels. Calculated transition probability and energy values, as well as LS-compositions obtained from the fitted parameters are presented.

74 ATOMIC AND MOLECULAR PHYSICS↗

Low earth orbit environmental effects on osmium and related optical thin-film coatings

A number of samples of optical thin film materials were flown on Shuttle flight STS-8 as part of an experiment to evaluate their interaction with residual atomic oxygen in low earth orbit. Osmium was selected because of its usefulness as a reflective optical coating for far-UV instruments and for confirmation of results from previous Shuttle flights in which such coatings disappeared. Reflectance data and photographic evidence are presented to support the hypothesis that the osmium disappearance is due to reaction with oxygen to form a volatile oxide. Platinum and iridium, which were included for comparison, fared much better.

Gull, T. R.↗

The role of nonmagnetic d{sup 0} vs. d{sup 10}B-type cations on the magnetic exchange interactions in osmium double perovskites

Polycrystalline samples of double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were synthesized by solid state reactions. They adopt the cubic double perovskite structures (space group, Fm-3m) with ordered B and Os arrangements. Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) show antiferromagnetic transitions at 93 K, 69 K, and 28 K, respectively. The Weiss-temperatures are −590 K for Ba{sub 2}ScOsO{sub 6}, −571 K for Ba{sub 2}YOsO{sub 6}, and −155 K for Ba{sub 2}InOsO{sub 6}. Sc{sup 3+} and Y{sup 3+} have the open-shell d{sup 0} electronic configuration, while In{sup 3+} has the closed-shell d{sup 10}. This indicates that a d{sup 0} B-type cation induces stronger overall magnetic exchange interactions in comparison to a d{sup 10}. Comparison of Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) to their Sr and Ca analogues shows that the structural distortions weaken the overall magnetic exchange interactions. - Graphical abstract: Magnetic properties of osmium double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were studied. Comparison of Ba{sub 2}BOsO{sub 6}indicates that a d{sup 0} B-type cation induces stronger overall magnetic exchange interactions in comparison to a d{sup 10}. - Highlights: • Magnetic properties of double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were studied. • A d{sup 0}B-type cation induces stronger magnetic interactions than a d{sup 10}. • Structural distortions weaken the overall Os{sup 5+}-Os{sup 5+} magnetic interactions.

36 MATERIALS SCIENCE↗

Relativistic Effects on a Metal–Metal Bond: Osmium Corrole Dimers

A series of metal–metal bonded osmium corrole dimers, {Os[T p XPC]} 2 , were synthesized in reasonably good yields (35–46%) via the interaction of the corresponding free-base meso -tris( p -X-phenyl)corroles (H 3 [T p XPC], X = CF 3 , H, CH 3 , and OCH 3 ), Os 3 (CO) 12 , and potassium carbonate in 1,2,4-trichlorobenzene under an inert atmosphere at 180 °C over several hours. The complexes are only the second class of Os corroles reported to date (the first being Os VI N corroles) and also the second class of metal–metal bonded metallocorrole dimers (the other being Ru corrole dimers). Comparison of the X-ray structures, redox potentials, and optical spectra of analogous Ru and Os corrole dimers, along with scalar-relativistic DFT calculations, has provided an experimentally calibrated account of relativistic effects in these complexes. Three of the Os corrole dimers (X = CF 3 , H, and OCH 3 ) were analyzed with single-crystal X-ray diffraction analysis, revealing inversion-related corrole rings with eclipsed Os–N bonds and Os–Os distances of ~2.24 Å that are ~0.06 Å longer than the Ru–Ru distances in the analogous Ru corrole dimers. Interestingly, a comparison of scalar-relativistic and nonrelativistic DFT calculations indicates that this difference in metal–metal bond distance does not, in fact, reflect a differential relativistic effect. Additionally, for a given corrole ligand, the Ru and Os corrole dimers exhibit nearly identical oxidation potentials but dramatically different reduction potentials, with the Os values ~0.5 V lower relative to Ru, suggesting that whereas oxidation occurs in a ligand-centered manner, reduction is substantially metal-centered, which indeed was confirmed by scalar-relativistic calculations. The calculations further indicate that approximately a third of the ~0.5 V difference in reduction potentials can be ascribed to relativity. The somewhat muted value of this relativistic effect appears to be related to the finding that reduction of an Os corrole dimer is not exclusively metal-based but that a significant amount of spin density is delocalized over to the corrole ligand; in contrast, reduction of an Ru corrole dimer occurs exclusively on the Ru–Ru linkage. For isoelectronic complexes, the Ru and Os corrole dimers exhibit substantially different UV–vis spectra. Furthermore, a key difference is a strong near-UV feature of the Os series, which in energy terms is blue-shifted by ~0.55 V relative to the analogous feature of the Ru series. TDDFT calculations suggest that this difference may be related to higher-energy Os(5d)-based LUMOs in the Os case relative to analogous MOs for Ru.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photophysical characterization of new osmium (II) photocatalysts for hydrohalic acid splitting

Two osmium(II) photocatalysts bearing a dicationic 4,4'-bis-(trimethylaminomethyl)-2,2'-bipyridine (tmam) ligand and 2,2'-bipyridine {[Os(bpy) 2 (tmam)] 4+ } or 4,4'-(CF 3 ) 2 -2,2'-bipyridine {[Os((CF3)2bpy) 2 (tmam)] 4+ } ancillary ligands were synthesized and characterized for application in HX splitting. Iodide titration studies in acetone solutions provided evidence for an in situ formed terionic complex with two iodide ions as evidenced by 1H NMR and UV-visible absorption spectroscopies, as well as by density functional theory calculations and natural bond order analysis. The photocatalyst [Os(bpy)2(tmam)] 4+ was shown to be inefficient in iodide oxidation. In contrast, visible light excitation of [Os((CF3)2bpy)2(tmam)]4+ led to rapid iodide oxidation, kq = 2.8 × 1011 M-1 s-1. The data reveal that Os(II) photocatalysts can be fine-tuned for application in HX splitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic and magnetic properties of quasi-one-dimensional osmium halide OsCl 4

Using ab initio density functional theory, we study the electronic and magnetic properties of the van der Waals chain material OsCl 4 . In the nonmagnetic state, a strongly anisotropic band structure was observed, in agreement with its anticipated one-dimensional crystal geometry. Based on Wannier functions, we found that the four electrons of the 5d Os atom form a low-spin S = 1 state, with a large crystal field between the d xz/yz and d xy orbitals, corresponding to a strong Jahn–Teller distortion (Q 3 < 0). As a consequence, the magnetic properties are mainly contributed by the d xz/yz states. Furthermore, when a Mott gap develops after the introduction of the Hubbard U and Hund coupling J, we found that the staggered spin order is the most likely magnetic state, namely, spins arranged as (↑-↓-↑-↓) with π wavevector along the chain. In addition, the energy differences between various spin states are small, suggesting a weak magnetic exchange coupling along the chain. Overall, our results provide guidance to experimentalists and theorists working on quasi-one-dimensional osmium halides chain materials.

36 MATERIALS SCIENCE↗

Exploring the hardness and high-pressure behavior of osmium and ruthenium-doped rhenium diboride solid solutions

Rhenium diboride (ReB 2 ) exhibits high differential strain due to its puckered boron sheets that impede shear deformation. Here, we demonstrate the use of solid solution formation to enhance the Vickers hardness and differential strain of ReB 2 . ReB 2 -structured solid solutions (Re 0.98 Os 0.02 B 2 and Re 0.98 Ru 0.02 B 2 , noted as “ReOsB 2 ” and “ReRuB 2 ”) were synthesized via arc-melting from the pure elements. In-situ high-pressure radial x-ray diffraction was performed in the diamond anvil cell to study the incompressibility and lattice strain of ReOsB 2 and ReRuB 2 up to ~56 GPa. Both solid solutions exhibit higher incompressibility and differential strain than pure ReB 2 . However, while all lattice planes are strengthened by doping osmium (Os) into the ReB 2 structure, only the weakest ReB 2 lattice plane is enhanced with ruthenium (Ru). These results are in agreement with the Vickers hardness measurements of the two systems, where higher hardness was observed in ReOsB 2 . The combination of high-pressure studies with experimentally observed hardness data provides lattice specific information about the strengthening mechanisms behind the intrinsic hardness enhancement of the ReB 2 system.

36 MATERIALS SCIENCE↗