Vanadium Electronic Configuration Determination From L2,3 Transition in V-oxide Compounds and Roscoelite.

We report on the electronic structure of vanadium in synthetic V-oxides and in natural roscoelite (V-rich phyllosilicate). This study applied electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM), combined with first-principle calculations, to (1) establish relationships between the V oxidation state and EELS L2,3 features and (2) better constrain the oxidation state and crystallographic siting of V in roscoelite, with implications for other V-bearing phyllosilicates. Both EELS measurements and band structure calculations show that the EELS L2/L3 ratio increases as the oxidation state of V increases. We establish a quantitative relationship between the V L2,3 near-edge structure and the V oxidation state by normalizing the L2 maximum peak intensity to the L3 peak intensity. By applying this method to roscoelite, we find that it hosts a mix of trivalent and tetravalent V distributed between the octahedral and tetrahedral sites with a V4+/ΣV = 0.6 ± 0.1. This relationship is applicable to measurements of V oxidation states in oxide and phyllosilicate minerals, which is useful for constraining the conditions of rock and mineral formation and has potential implications for metal extraction from phyllosilicate ores.

Destructive Processing of Silicon Carbide Grains: Experimental Insights into the Formation of Interstellar Fullerenes and Carbon Nanotubes.

The detection of the fullerenes C60 and C70 in the interstellar medium (ISM) has transformed our understanding of chemical complexity in space. These discoveries also raise the possibility for the presence of even larger molecules in astrophysical environments. Here we report in situ heating of analog silicon carbide (SiC) presolar grains using transmission electron microscopy (TEM). These heating experiments are designed to simulate the temperature conditions occurring in post-AGB stellar envelopes. Our experimental findings reveal that heating the analog SiC grains to the point of decomposition initially yields hemispherical C60-sized nanostructures, with five- and six-membered rings, which transform into multiwalled carbon nanotubes (MWCNTs) if held isothermally >2 min. These MWCNTs are certainly larger than any of the currently observed interstellar fullerene species, both in overall size and number of C atoms. These experimental simulations suggest that such MWCNTs are likely to form in post-AGB circumstellar material, where the structures, along with the smaller fullerenes, are subsequently injected into the ISM.

A nanometric window on fullerene formation in the interstellar medium: Insights from molecular dynamics studies.

Understanding the fundamental mechanisms that underlie the synthesis of fullerene molecules in the interstellar medium (ISM) and in the environments of astrophysical objects is an open question. In this regard, using classical molecular dynamics, we demonstrate the possibility of in situ formation of fullerene molecules, such as C60 from graphite, which is known to occur in the ISM, in particular, circumstellar environments. Specifically, when graphite is subjected to thermal and mechanical stimuli that are typical of circumstellar shells, we find that the graphite sheet edges undergo significant restructuring and curling, leading to edge-induced interlayer-interactions and formation of mechanically strained five-membered-ring structural units. These units serve as precursors for the formation of fullerene structures, such as pristine and metastable C60 molecules. The pathways leading to molecular C60 formation consist of a series of steps that involve bond-breakage and subsequent local rearrangement of atoms, with the activation energy barriers of the rate-limiting step(s) being comparable to the energetics of Stone-Wales rearrangement reactions. The identified chemical pathways provide fundamental insights into the mechanisms that underlie C60 formation. Moreover, they clearly demonstrate that top-down synthesis of C60 from graphitic sources is a viable synthesis route at conditions pertaining to circumstellar matter.

The Fe/S ratio of pyrrhotite group sulfides in chondrites: An indicator of oxidation and implications for return samples from asteroids Ryugu and Bennu.

Determining compositional trends among individual minerals is key to understanding the thermodynamic conditions under which they formed and altered, and is also essential to maximizing the scientific value of small extraterrestrial samples, including returned samples and meteorites. Here we report the chemical compositions of Fe-sulfides, focusing on the pyrrhotite-group sulfides, which are ubiquitous in chondrites and are sensitive indicators of formation and alteration conditions in the protoplanetary disk and in small Solar System bodies. Our data show that while there are trends with the at.% Fe/S ratio of pyrrhotite with thermal and aqueous alteration in some meteorite groups, there is a universal trend between the Fe/S ratio and degree of oxidation. Relatively reducing conditions led to the formation of troilite during: (1) chondrule formation in the protoplanetary disk (i.e., pristine chondrites) and (2) parent body thermal alteration (i.e., LL4 to LL6, CR1, CM, and CY chondrites). Oxidizing and sulfidizing conditions led to the formation of Fe-depleted pyrrhotite with low Fe/S ratios during: (1) aqueous alteration (i.e., CM and CI chondrites), and (2) thermal alteration (i.e., CK and R chondrites). The presence of troilite in highly aqueously altered carbonaceous chondrites (e.g., CY, CR1, and some CM chondrites) indicates they were heated after aqueous alteration. The presence of troilite, Fe-depleted pyrrhotite, or pyrite in a chondrite can provide an estimate of the oxygen and sulfur fugacities at which it was formed or altered. The data reported here can be used to estimate the oxygen fugacity of formation and potentially the aqueous and/or thermal histories of sulfides in extraterrestrial samples, including those returned by the Hayabusa2 mission and due to be returned by the OSIRIS-REx mission in the near future.

Petrographic and compositional indicators of formation and alteration conditions from LL chondrite sulfides.

Sulfide minerals occur in many types of extraterrestrial samples and are sensitive indicators of the conditions under which they formed or were subsequently altered. Here we report that chemical and petrographic analyses of Fe,Ni sulfides can be used to determine the metamorphic type of the host LL chondrite, and constrain their alteration conditions. Our data show that the major- and minor-element compositions of the pyrrhotite-group sulfides (dominantly troilite) and pentlandite vary with degree of thermal metamorphism experienced by their host chondrite. We find that Fe,Ni sulfides in LL3 chondrites formed during chondrule cooling prior to accretion, whereas those in LL4 to LL6 chondrites formed during cooling after thermal metamorphism in the parent body, in agreement with previous work. High degrees of shock (i.e., ≥S5) caused distinct textural, structural, and compositional changes that can be used to identify highly shocked samples. Distinct pyrrhotite-pentlandite textures and minerals present in Appley Bridge (LL6) suggest that they cooled more slowly and therefore occurred at greater depth(s) in the host parent body than those of the other metamorphosed LL chondrites studied here. Sulfides in all LL chondrites studied formed under similar sulfur fugacities, and the metamorphosed LL chondrites formed under similar oxygen fugacities. The data reported here can be applied to the study of other LL chondrites and to sulfides in samples of asteroid Itokawa returned by the Hayabusa mission in order to learn more about the formation and alteration history of the LL chondrite parent body.

Graphene mediated self-assembly of fullerene nanorods.

A simple procedure for solution-based self-assembly of C60 fullerene nanorods on graphene substrates is presented. Using a combination of electron microscopy, X-ray diffraction and Raman spectroscopy, it is shown that the size, shape and morphology of the nanorods can be suitably modified by controlling the kinetics of self-assembly.

Mineralogy and petrology of comet 81P/Wild 2 nucleus samples.

The bulk of the comet 81P/Wild 2 (hereafter Wild 2) samples returned to Earth by the Stardust spacecraft appear to be weakly constructed mixtures of nanometer-scale grains, with occasional much larger (over 1 micrometer) ferromagnesian silicates, Fe-Ni sulfides, Fe-Ni metal, and accessory phases. The very wide range of olivine and low-Ca pyroxene compositions in comet Wild 2 requires a wide range of formation conditions, probably reflecting very different formation locations in the protoplanetary disk. The restricted compositional ranges of Fe-Ni sulfides, the wide range for silicates, and the absence of hydrous phases indicate that comet Wild 2 experienced little or no aqueous alteration. Less abundant Wild 2 materials include a refractory particle, whose presence appears to require radial transport in the early protoplanetary disk.

Determination of interface atomic structure and its impact on spin transport using Z-contrast microscopy and density-functional theory.

We combine Z-contrast scanning transmission electron microscopy with density-functional-theory calculations to determine the atomic structure of the interface in spin-polarized light-emitting diodes. A 44% increase in spin-injection efficiency occurs after a low-temperature anneal, which produces an ordered, coherent interface consisting of a single atomic plane of alternating Fe and As atoms. First-principles transport calculations indicate that the increase in spin-injection efficiency is due to the abruptness and coherency of the annealed interface.