Tantalum sound velocity under shock compression

We used several variations of the shock compression method to measure the longitudinal sound velocity of shocked tantalum over the pressure range 37–363 GPa with a typical uncertainty of 1.0%%. These data are consistent with Ta remaining in the bcc phase along the principal Hugoniot from ambient pressure to ≈300 GPa, at which pressure melting occurs. These data also do not support the putative melting phenomena reported below 100 GPa in some static compression experiments

Tantalum sound velocity under shock compression

We used several variations of the shock compression method to measure the longitudinal sound velocity of shocked tantalum over the pressure range 37–363 GPa with a typical uncertainty of 1.0%%. These data are consistent with Ta remaining in the bcc phase along the principal Hugoniot from ambient pressure to ≈300 GPa, at which pressure melting occurs. These data also do not support the putative melting phenomena reported below 100 GPa in some static compression experiments

The c2d Spitzer Spectroscopic Survey of Ices Around Low-Mass Young Stellar Objects. IV. NH3 and CH3OH

NH3 and CH3OH are key molecules in astrochemical networks leading to the formation of more complex N- and O-bearing molecules, such as CH3CN and HCOOCH3. Despite a number of recent studies, little is known about their abundances in the solid state. (...) In this work, we investigate the ~ 8-10 micron region in the Spitzer IRS (InfraRed Spectrograph) spectra of 41 low-mass young stellar objects (YSOs). These data are part of a survey of interstellar ices in a sample of low-mass YSOs studied in earlier papers in this series. We used both an empirical and a local continuum method to correct for the contribution from the 10 micron silicate absorption in the recorded spectra. In addition, we conducted a systematic laboratory study of NH3- and CH3OH-containing ices to help interpret the astronomical spectra. We clearly detect a feature at ~9 micron in 24 low-mass YSOs. Within the uncertainty in continuum determination, we identify this feature with the NH3 nu_2 umbrella mode, and derive abundances with respect to water between ~2 and 15%. Simultaneously, we also revisited the case of CH3OH ice by studying the nu_4 C-O stretch mode of this molecule at ~9.7 micron in 16 objects, yielding abundances consistent with those derived by Boogert et al. 2008 (hereafter paper I) based on a simultaneous 9.75 and 3.53 micron data analysis. Our study indicates that NH3 is present primarily in H2O-rich ices, but that in some cases, such ices are insufficient to explain the observed narrow FWHM. The laboratory data point to CH3OH being in an almost pure methanol ice, or mixed mainly with CO or CO2, consistent with its formation through hydrogenation on grains. Finally, we use our derived NH3 abundances in combination with previously published abundances of other solid N-bearing species to find that up to 10-20 % of nitrogen is locked up in known ices.Comment: 31 pages, 15 figures, accepted for publication in Ap

Imaging Shock Waves in Diamond with Both High Temporal and Spatial Resolution at an XFEL

The advent of hard x-ray free-electron lasers (XFELs) has opened up a variety of scientific opportunities in areas as diverse as atomic physics, plasma physics, nonlinear optics in the x-ray range and protein crystallography. In this article, we access a new field of science by measuring quantitatively the local bulk properties and dynamics of matter under extreme conditions, in this case by using the short XFEL pulse to image an elastic compression wave in diamond. The elastic wave was initiated by an intense optical laser pulse and was imaged at different delay times after the optical pump pulse using magnified x-ray phase-contrast imaging. The temporal evolution of the shock wave can be monitored, yielding detailed information on shock dynamics, such as the shock velocity, the shock front width and the local compression of the material. The method provides a quantitative perspective on the state of matter in extreme conditions

Manganese K-Edge X-Ray Absorption Spectroscopy as a Probe of the Metal–Ligand Interactions in Coordination Compounds

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Manganese K-Edge X-Ray Absorption Spectroscopy as a Probe of the Metal–Ligand Interactions in Coordination Compounds

A series of manganese coordination compounds has been investigated by X-ray absorption spectroscopy (XAS). The K-pre-edge spectra are interpreted with the aid of time-dependent density functional theory (TD-DFT). This method was calibrated for the prediction of manganese K-pre-edges with different functionals. Moreover the nature of all observed features could be identified and classified according to the corresponding set of acceptor orbitals, either 1s to 3d transitions or metal-to-ligand charge transfer (MLCT) bands. The observable MLCT bands are further divided into features that correspond to transitions into empty π* orbitals of π-donor ligands and those of π-acceptor ligands. The ability to computationally reproduce the observed features at the correct relative transition energy is strongly dependent on the nature of the transition. A detailed analysis of the electronic structure of a series of Mn coordination compounds reveals that the different classes of observable transitions provide added insight into metal–ligand bonding interactions

The Protonation States of Oxo-Bridged Mn(IV) Dimers Resolved by Experimental and Computational Mn K Pre-Edge X-ray Absorption Spectroscopy

In nature, the protonation of oxo bridges is a commonly encountered mechanism for fine-tuning chemical properties and reaction pathways. Often, however, the protonation states are difficult to establish experimentally. This is of particular importance in the oxygen evolving complex of Photosystem II, where identification of the bridging oxo protonation states is one of the essential requirements toward unraveling the mechanism. In order to establish a combined experimental and theoretical protocol for the determination of protonation states, we have systematically investigated a series of Mn model complexes by Mn K pre-edge X-ray absorption spectroscopy. An ideal test case for selective bis-μ-oxo-bridge protonation in a Mn-dimer is represented by the system [Mn(IV)(2)(salpn)(2)(μ-OH((n)))(2)]((n+)). Although the three species [Mn(IV)(2)(salpn)(2)(μ-O)(2)], [Mn(IV)(2)(salpn)(2)(μ-O)(μ-OH)](+) and [Mn(IV)(2)(salpn)(2)(μ-OH)(2)](2+) differ only in the protonation of the oxo bridges, they exhibit distinct differences in the pre-edge region while maintaining the same edge energy. The experimental spectra are correlated in detail to theoretical ly calculated spectra. A time-dependent density functional theory approach for calculating the pre-edge spectra of molecules with multiple metal centers is presented, using both high-spin (HS) and broken-symmetry (BS) electronic structure solutions. The most intense pre-edge transitions correspond to an excitation of the Mn-1s core electrons into the unoccupied orbitals of local e(g) character (d(z(2)) and d(xy) based in the chosen coordinate system). The lowest by energy experimental feature is dominated by excitations of 1s-α electrons and the second observed feature is primarily attributed to 1s-β electron excitations. The observed energetic separation is due to spin polarization effects in spin-unrestricted density functional theory and models final state multiplet effects. The effects of spin polarization on the calculated Mn K pre-edge spectra, in both the HS and BS solutions, are discussed in terms of the strength of the antiferromagnetic coupling and associated changes in the covalency of Mn-O bonds. The information presented in this paper is complemented with the X-ray emission spectra of the same compounds published in an accompanying paper. Taken together, the two studies provide the foundation for a better understanding of the X-ray spectroscopic data of the oxygen evolving complex (OEC) in Photosystem II