Heterogeneous distribution of Al-26 at the birth of the Solar System

It is believed that Al-26, a short-lived (t1/2 = 0.73 Ma) and now extinct radionuclide, was uniformly distributed in the nascent Solar System with the initial Al-26/Al-27 ratio of ~5.2\times10-5, suggesting its external stellar origin. However, the stellar source of Al-26 and the manner in which it was injected into the solar system remain controversial: the Al-26 could have been produced by an asymptotic giant branch star, a supernova, or a Wolf-Rayet star and injected either into the protosolar molecular cloud or protoplanetary disk. Corundum (Al2O3) is thermodynamically predicted to be the first condensate from a cooling gas of solar composition. Here we show that micron-sized corundum condensates from O-16-rich gas (Big Delta O-17 ~ -25%) of solar composition recorded heterogeneous distribution of Al-26 at the birth of the solar system: the inferred initial Al-26/Al-27 ratio ranges from ~6.5x10-5 to <2x10-6; ~50% of the corundum grains measured are Al-26-poor. Other Al-26-poor, O-16-rich refractory objects include grossite (CaAl4O7)- and hibonite(CaAl12O19)-rich calcium-aluminum-rich inclusions (CAIs) in CH chondrites, platy hibonite crystals in CM chondrites, and FUN (fractionation and unidentified nuclear isotopic anomalies) CAIs in CV, CO, and CR chondrites. Considering the apparently early and short duration (<0.3 Ma) of condensation of refractory O-16-rich solids in the solar system, we infer that Al-26 was injected into the collapsing protosolar molecular cloud and later homogenized in the protoplanetary disk. The apparent lack of correlation between Al-26 abundance and O-isotope compositions of corundum grains put important constraints on the stellar source of Al-26 in the solar system.Comment: Astrophysical Journal Letters 733, L3

Optical constants of refractory oxides at high temperatures

Many cosmic dust species, among them refractory oxides, form at temperatures higher than 300 K. Nevertheless, most astrophysical studies are based on the room-temperature optical constants of solids, such as corundum and spinel. A more realistic approach is needed for these materials, especially in the context of modeling late-type stars. We aimed at deriving sets of optical constants of selected, astrophysically relevant oxide dust species with high melting points. A high-temperature-high-pressure-cell and a Fourier-transform spectrometer were used to measure reflectance spectra of polished samples. For corundum (alpha-Al$_2$O$_3$), spinel (MgAl$_2$O$_4$), and alpha-quartz (SiO$_2$), temperature-dependent optical constants were measured from 300 K up to more than 900 K. Small particle spectra were also calculated from these data. All three examined oxides show a significant temperature dependence of their mid-IR bands. For the case of corundum, we find that the 13$\mu$m emission feature - seen in the IR spectra of many AGB stars - can very well be assigned to this mineral species. The best fit of the feature is achieved with oblate corundum grains at mean temperatures around 550 K. Spinel remains a viable carrier of the 13$\mu$m feature as well, but only for T < 300 K and nearly spherical grain shapes. Under such circumstances, spinel grains may also account for the 31.8$\mu$m band that is frequently seen in sources of the 13$\mu$m feature and which has not yet been identified with certainty.Comment: Astronomy & Astrophysics, accepted, 26 February 2013. Article with 18 pages and 15 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

Dust in the wind: Crystalline silicates, corundum and periclase in PG 2112+059

We have determined the mineralogical composition of dust in the Broad Absorption Line (BAL) quasar PG 2112+059 using mid-infrared spectroscopy obtained with the Spitzer Space Telescope. From spectral fitting of the solid state features, we find evidence for Mg-rich amorphous silicates with olivine stoichiometry, as well as the first detection of corundum (Al_2O_3) and periclase (MgO) in quasars. This mixed composition provides the first direct evidence for a clumpy density structure of the grain forming region. The silicates in total encompass 56.5% of the identified dust mass, while corundum takes up 38 wt.%. Depending on the choice of continuum, a range of mass fractions is observed for periclase ranging from 2.7% in the most conservative case to 9% in a less constrained continuum. In addition, we identify a feature at 11.2 micron as the crystalline silicate forsterite, with only a minor contribution from polycyclic aromatic hydrocarbons. The 5% crystalline silicate fraction requires high temperatures such as those found in the immediate quasar environment in order to counteract rapid destruction from cosmic rays.Comment: 2 figure

Fe-substituted mullite powders for the in situ synthesis of carbon nanotubes by catalytic chemical vapor deposition

Powders of iron-substituted mullite were prepared by combustion and further calcination in air at different temperatures. A detailed study involving notably Mo¨ssbauer spectroscopy showed that the Fe3+ ions are distributed between the mullite phase and a corundum phase that progressively dissolves into mullite upon the increase in calcination temperature. Carbon nanotube-Fe-mullite nanocomposites were prepared for the first time by a direct method involving a reduction of these powders in H2-CH4 and without any mechanical mixing step. The carbon nanotubes formed by the catalytic decomposition of CH4 on the smallest metal particles are mostly double-walled and multiwalled, although some carbon nanofibers are also observed

Uncovering the mechanism of the impurity-selective Mott transition in paramagnetic V2_{2}O3_{3}

While the phase diagrams of the one- and multi-orbital Hubbard model have been well studied, the physics of real Mott insulators is often much richer, material dependent, and poorly understood. In the prototype Mott insulator V$_{2}$O$_{3}$, chemical pressure was initially believed to explain why the paramagnetic-metal to antiferromagnetic-insulator transition temperature is lowered by Ti doping while Cr doping strengthens correlations, eventually rendering the high-temperature phase paramagnetic insulating. However, this scenario has been recently shown both experimentally and theoretically to be untenable. Based on full structural optimization, we demonstrate via the charge self-consistent combination of density functional theory and dynamical mean-field theory that changes in the V$_{2}$O$_{3}$ phase diagram are driven by defect-induced local symmetry breakings resulting from dramatically different couplings of Cr and Ti dopants to the host system. This finding emphasizes the high sensitivity of the Mott metal-insulator transition to the local environment and the importance of accurately accounting for the one-electron Hamiltonian, since correlations crucially respond to it.Comment: 5 pages, 5 figures, supplementary informatio