41 research outputs found
X-ray absorption spectroscopy systematics at the tungsten L-edge
A series of mononuclear six-coordinate tungsten compounds spanning formal oxidation states from 0 to +VI, largely in a ligand environment of inert chloride and/or phosphine, has been interrogated by tungsten L-edge X-ray absorption spectroscopy. The L-edge spectra of this compound set, comprised of [W<sup>0</sup>(PMe<sub>3</sub>)<sub>6</sub>], [W<sup>II</sup>Cl<sub>2</sub>(PMePh<sub>2</sub>)<sub>4</sub>], [W<sup>III</sup>Cl<sub>2</sub>(dppe)<sub>2</sub>][PF<sub>6</sub>] (dppe = 1,2-bis(diphenylphosphino)ethane), [W<sup>IV</sup>Cl<sub>4</sub>(PMePh<sub>2</sub>)<sub>2</sub>], [W<sup>V</sup>(NPh)Cl<sub>3</sub>(PMe<sub>3</sub>)<sub>2</sub>], and [W<sup>VI</sup>Cl<sub>6</sub>] correlate with formal oxidation state and have usefulness as references for the interpretation of the L-edge spectra of tungsten compounds with redox-active ligands and ambiguous electronic structure descriptions. The utility of these spectra arises from the combined correlation of the estimated branching ratio (EBR) of the L<sub>3,2</sub>-edges and the L<sub>1</sub> rising-edge energy with metal Z<sub>eff</sub>, thereby permitting an assessment of effective metal oxidation state. An application of these reference spectra is illustrated by their use as backdrop for the L-edge X-ray absorption spectra of [W<sup>IV</sup>(mdt)<sub>2</sub>(CO)<sub>2</sub>] and [W<sup>IV</sup>(mdt)<sub>2</sub>(CN)<sub>2</sub>]<sup>2–</sup> (mdt<sup>2–</sup> = 1,2-dimethylethene-1,2-dithiolate), which shows that both compounds are effectively W<sup>IV</sup> species. Use of metal L-edge XAS to assess a compound of uncertain formulation requires: 1) Placement of that data within the context of spectra offered by unambiguous calibrant compounds, preferably with the same coordination number and similar metal ligand distances. Such spectra assist in defining upper and/or lower limits for metal Z<sub>eff</sub> in the species of interest; 2) Evaluation of that data in conjunction with information from other physical methods, especially ligand K-edge XAS; 3) Increased care in interpretation if strong π-acceptor ligands, particularly CO, or π-donor ligands are present. The electron-withdrawing/donating nature of these ligand types, combined with relatively short metal-ligand distances, exaggerate the difference between formal oxidation state and metal Z<sub>eff</sub> or, as in the case of [W<sup>IV</sup>(mdt)<sub>2</sub>(CO)<sub>2</sub>], add other subtlety by modulating the redox level of other ligands in the coordination sphere
Infrared Absorption Investigations Confirm the Extraterrestrial Origin of Carbonado-Diamonds
The first complete infrared FTIR absorption spectra for carbonado-diamond
confirm the interstellar origin for the most enigmatic diamonds known as
carbonado. All previous attempts failed to measure the absorption of
carbonado-diamond in the most important IR-range of 1000-1300 cm-1 (10.00-7.69
micro-m.) because of silica inclusions. In our investigation, KBr pellets were
made from crushed silica-free carbonado-diamond and thin sections were also
prepared. The 100 to 1000 times brighter synchrotron infrared radiation permits
a greater spatial resolution. Inclusions and pore spaces were avoided and/or
sources of chemical contamination were removed. The FTIR spectra of
carbonado-diamond mostly depict the presence of single nitrogen impurities, and
hydrogen. The lack of identifiable nitrogen aggregates in the infrared spectra,
the presence of features related to hydrocarbon stretch bonds, and the
resemblance of the spectra to CVD and presolar diamonds indicate that
carbonado-diamonds formed in a hydrogen-rich interstellar environment. This is
consistent with carbonado-diamond being sintered and porous, with extremely
reduced metals, metal alloys, carbides and nitrides, light carbon isotopes,
surfaces with glassy melt-like patinas, deformation lamellae, and a complete
absence of primary, terrestrial mineral inclusions. The 2.6-3.8 billion year
old fragmented body was of asteroidal proportions
Production of dust by massive stars at high redshift
The large amounts of dust detected in sub-millimeter galaxies and quasars at
high redshift pose a challenge to galaxy formation models and theories of
cosmic dust formation. At z > 6 only stars of relatively high mass (> 3 Msun)
are sufficiently short-lived to be potential stellar sources of dust. This
review is devoted to identifying and quantifying the most important stellar
channels of rapid dust formation. We ascertain the dust production efficiency
of stars in the mass range 3-40 Msun using both observed and theoretical dust
yields of evolved massive stars and supernovae (SNe) and provide analytical
expressions for the dust production efficiencies in various scenarios. We also
address the strong sensitivity of the total dust productivity to the initial
mass function. From simple considerations, we find that, in the early Universe,
high-mass (> 3 Msun) asymptotic giant branch stars can only be dominant dust
producers if SNe generate <~ 3 x 10^-3 Msun of dust whereas SNe prevail if they
are more efficient. We address the challenges in inferring dust masses and
star-formation rates from observations of high-redshift galaxies. We conclude
that significant SN dust production at high redshift is likely required to
reproduce current dust mass estimates, possibly coupled with rapid dust grain
growth in the interstellar medium.Comment: 72 pages, 9 figures, 5 tables; to be published in The Astronomy and
Astrophysics Revie