Harvard College OSO-IV pointed experiment - An analysis of the malfunction during orbit 637

Telemetered malfunction data analysis from orbiting OSO- 4 implicating transforme

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Temperature-dependent Raman scattering of DyScO3 and GdScO3 single crystals

We report a temperature-dependent Raman scattering investigation of DyScO3 and GdScO3 single crystals from room temperature up to 1200 {\deg}C. With increasing temperature, all modes decrease monotonously in wavenumber without anomaly, which attests the absence of a structural phase transition. The high temperature spectral signature and extrapolation of band positions to higher temperatures suggest a decreasing orthorhombic distortion towards the ideal cubic structure. Our study indicates that this orthorhombic-to-cubic phase transition is close to or higher than the melting point of both rare-earth scandates (\approx 2100 {\deg}C), which might exclude the possibility of the experimental observation of such a phase transition before melting. The temperature-dependent shift of Raman phonons is also discussed in the context of thermal expansion

Post-spinel transformations and equation of state in ZnGa2O4: Determination at high-pressure by in situ x-ray diffraction

Room temperature angle-dispersive x-ray diffraction measurements on spinel ZnGa2O4 up to 56 GPa show evidence of two structural phase transformations. At 31.2 GPa, ZnGa2O4 undergoes a transition from the cubic spinel structure to a tetragonal spinel structure similar to that of ZnMn2O4. At 55 GPa, a second transition to the orthorhombic marokite structure (CaMn2O4-type) takes place. The equation of state of cubic spinel ZnGa2O4 is determined: V0 = 580.1(9) A3, B0 = 233(8) GPa, B0'= 8.3(4), and B0''= -0.1145 GPa-1 (implied value); showing that ZnGa2O4 is one of the less compressible spinels studied to date. For the tetragonal structure an equation of state is also determined: V0 = 257.8(9) A3, B0 = 257(11) GPa, B0'= 7.5(6), and B0''= -0.0764 GPa-1 (implied value). The reported structural sequence coincides with that found in NiMn2O4 and MgMn2O4.Comment: 20 pages, 4 figures, 2 Table

Stratigraphic Architecture and Sediment Facies of the Western Oak Ridges Moraine, Humber River Watershed, Southern Ontario

The Oak Ridges Moraine in southern Ontario is a ca. 160 km long east-west trending ridge of sand and gravel situated north of Lake Ontario. Study of the Oak Ridges Moraine in the Humber River watershed was undertaken to assess its role in the groundwater system of the buried Laurentian Valley. The Oak Ridges Moraine is interpreted to have been deposited in three stages. Stage I records rapid deposition from hyperconcentrated flows where tunnel channels discharged into a subglacial lake in the Lake Ontario basin. Low-energy basin sedimentation of Stage II was in a subglacial and ice-contact setting of a highly crevassed ice sheet. Stage III sedimentation is characterized by rapid facies changes associated with esker, subaqueous fan, and basinal sedimentation. Detailed sediment analysis challenges the concept that the Oak Ridges Moraine was deposited principally from seasonal meltwater discharges, climatic modulated ice-marginal fluctuations, or in an interlobate position. Instead it is interpreted to have formed in response to late-glacial ice sheet events associated with subglacial meltwater ponding, episodic and catastrophic subglacial meltwater discharge, and subsequent seasonal meltwater discharge. The moraine probably formed as the glacial-hydraulic system re-equilibrated to the presence of a thinned, grounded ice shelf and a subglacial lake in the Lake Ontario basin.La moraine de Oak Ridges, sud de l’Ontario, est une crête de sable et de gravier orientée est-ouest d’une longueur de 160 km au nord du lac Ontario. L’étude de la moraine de Oak Ridges dans le bassin de la rivière Humber permet de comprendre son rôle dans le système de drainage de la vallée Laurentienne. La moraine de Oak Ridges a été édifiée en trois phases. La phase I consiste en une sédimentation rapide par hyperconcentration des écoulements, où les chenaux en tunnel se déversent dans un lac sous-glaciaire du lac Ontario. Le bassin de sédimentation de faible énergie de la phase II est sous-glaciaire et touche à un inlandsis ayant d’importantes crevasses. La phase III se caractérise par un changement de faciès très rapide, par la présence d’eskers, de cônes aquatiques et de bassins sédimentaires. Les analyses sédimentaires détaillées ébranlent l’hypothèse que la moraine de Oak Ridges ait été formée par la fonte des glaces saisonnière, les fluctuations climatiques près des marges glaciaires, ou dans une position interlobaire. Notre interprétation indique plutôt qu’elle a été mise en place en réponse à des événements de fonte sous-glaciaire de nature épisodique et catastrophique, et par des apports subséquents d’eau de fonte saisonnière. La moraine s’est probablement formée lors de la ré-équilibration du système glacio-hydraulique en présence d’un inlandsis mince, en contact avec le substrat et alimentant un lac sous-glaciaire dans le bassin du lac Ontario

Pressure Dependence of the Magnetic Anisotropy in the "Single-Molecule Magnet" [Mn4O3Br(OAc)3(dbm)3]

The anisotropy splitting in the ground state of the single-molecule magnet [Mn4O3Br(OAc)3(dbm)3] is studied by inelastic neutron scattering as a function of hydrostatic pressure. This allows a tuning of the anisotropy and thus the energy barrier for slow magnetisation relaxation at low temperatures. The value of the negative axial anisotropy parameter $D_{\rm cluster}$ changes from -0.0627(1) meV at ambient to -0.0603(3) meV at 12 kbar pressure, and in the same pressure range the height of the energy barrier between up and down spins is reduced from 1.260(5) meV to 1.213(9) meV. Since the $\rm Mn-Br$ bond is significantly softer and thus more compressible than the $\rm Mn-O$ bonds, pressure induces a tilt of the single ion Mn$^{3+}$ anisotropy axes, resulting in the net reduction of the axial cluster anisotropy.Comment: 4 pages, 3 figure

Experimental evidence of thermal fluctuations on the X-ray absorption near-edge structure at the aluminum K-edge

After a review of temperature-dependent experimental x-ray absorption near-edge structure (XANES) and related theoretical developments, we present the Al K-edge XANES spectra of corundum and beryl for temperature ranging from 300K to 930K. These experimental results provide a first evidence of the role of thermal fluctuation in XANES at the Al K-edge especially in the pre-edge region. The study is carried out by polarized XANES measurements of single crystals. For any orientation of the sample with respect to the x-ray beam, the pre-edge peak grows and shifts to lower energy with temperature. In addition temperature induces modifications in the position and intensities of the main XANES features. First-principles DFT calculations are performed for both compounds. They show that the pre-edge peak originates from forbidden 1s to 3s transitions induced by vibrations. Three existing theoretical models are used to take vibrations into account in the absorption cross section calculations: i) an average of the XANES spectra over the thermal displacements of the absorbing atom around its equilibrium position, ii) a method based on the crude Born-Oppenheimer approximation where only the initial state is averaged over thermal displacements, iii) a convolution of the spectra obtained for the atoms at the equilibrium positions with an approximate phonon spectral function. The theoretical spectra so obtained permit to qualitatively understand the origin of the spectral modifications induced by temperature. However the correct treatment of thermal fluctuation in XANES spectroscopy requires more sophisticated theoretical tools

High-pressure investigations of CaTiO3 up to 60 GPa using X-ray diffraction and Raman spectroscopy

In this work, we investigate calcium titanate (CaTiO3 - CTO) using X-ray diffraction and Raman spectroscopy up to 60 and 55 GPa respectively. Both experiments show that the orthorhombic Pnma structure remains stable up to the highest pressures measured, in contradiction to ab-initio predictions. A fit of the compression data with a second-order Birch-Murnaghan equation of state yields a bulk modulus K0 of 181.0(6) GPa. The orthorhombic distortion is found to increase slightly with pressure, in agreement with previous experiments at lower pressures and the general rules for the evolution of perovskites under pressure. High-pressure polarized Raman spectra also enable us to clarify the Raman mode assignment of CTO and identify the modes corresponding to rigid rotation of the octahedra, A-cation shifts and Ti-O bond stretching. The Raman signature is then discussed in terms of compression mechanisms.Comment: 11 pages, 6 figures, 4 table

High-pressure structural investigation of several zircon-type orthovanadates

Room temperature angle-dispersive x-ray diffraction measurements on zircon-type EuVO4, LuVO4, and ScVO4 were performed up to 27 GPa. In the three compounds we found evidence of a pressure-induced structural phase transformation from zircon to a scheelite-type structure. The onset of the transition is near 8 GPa, but the transition is sluggish and the low- and high-pressure phases coexist in a pressure range of about 10 GPa. In EuVO4 and LuVO4 a second transition to a M-fergusonite-type phase was found near 21 GPa. The equations of state for the zircon and scheelite phases are also determined. Among the three studied compounds, we found that ScVO4 is less compressible than EuVO4 and LuVO4, being the most incompressible orthovanadate studied to date. The sequence of structural transitions and compressibilities are discussed in comparison with other zircon-type oxides.Comment: 34 pages, 2 Tables, 11 Figure

EXAFS study of lead-free relaxor ferroelectric BaTi(1-x)Zr(x)O3 at the Zr K-edge

Extended X-ray absorption fine structure (EXAFS) experiments at the Zr K-edge were carried out on perovskite relaxor ferroelectrics BaTi(1-x)Zr(x)O3 (BTZ) (x = 0.25, 0.30, 0.35), and on BaZrO3 for comparison. Structural information up to 4.5 A around the Zr atoms is obtained, revealing that the local structure differs notably from the average Pm-3m cubic structure deduced from X-ray diffraction. In particular, our results show that the distance between Zr atoms and their first oxygen neighbors is independent of the Zr substitution rate x and equal to that measured in BaZrO3, while the X-ray cubic cell parameter increases linearly with x. Furthermore, we show that the Zr atoms tend to segregate in Zr-rich regions. We propose that the relaxor behavior in BTZ is linked to random elastic fields generated by this particular chemical arrangement, rather than to random electric fields as is the case in most relaxors.Comment: 13 pages, 12 figures, 4 tables. Submitted to Phys. Rev.