Bulk and molecular compressibilities of organic-inorganic hybrids [(CH3)4N]2MnX4 (X = Cl, Br); role of intermolecular interactions.

This work reports an X-ray diffraction, X-ray absorption, and Raman spectroscopy study of [(CH3)4N]2MnX4 (X = Cl, Br) under pressure. We show that both compounds share a similar phase diagram with pressure. A P21/c monoclinic structure describes precisely the [(CH3)4N]2MnCl4 crystal in the 0.1-6 GPa range, prior to crystal decomposition and amorphization, while [(CH3)4N]2MnBr4 can be described by a Pmcn orthorhombic structure in its stability pressure range of 0-3 GPa. These materials are attractive systems for pressure studies since they are readily compressible through the weak interaction between organic/inorganic [(CH3)4N⁺/MnX4²â»] tetrahedra through hydrogen bonds and contrast with the small compressibility of both tetrahedra. Here we determine the equation-of-state (EOS) of each crystal and compare it with the corresponding local EOS of the MnX4²â» and (CH3)4N⁺ tetrahedra, the compressibility of which is an order and 2 orders of magnitude smaller than the crystal compressibility, respectively, in both chloride and bromide. The variations of the Mn-Cl bond distance obtained by extended X-ray absorption fine structure and the frequency of the totally symmetric ν1(A1) Raman mode of MnCl4²â» with pressure in [(CH3)4N]2MnCl4 allowed us to determine the associated Grüneisen parameter (γ(loc) = 1.15) and hence an accurate local EOS. On the basis of a local compressibility model, we obtained the Grüneisen parameters and corresponding variations of the intramolecular Mn­Br and C­N bond distances of MnBr4²â» (γ(loc) = 1.45) and (CH3)4N⁺ (γ(loc) = 3.0) in [(CH3)4N]2MnBr4.

Synthesis of a novel zeolite through a pressure-induced reconstructive phase transition process.

The first pressure-induced solid-phase synthesis of a zeolite has been found through compression of a common zeolite, ITQ-29 (see scheme, Si yellow, O red). The new microporous structure, ITQ-50, has a unique structure and improved performance for propene/propane separation with respect the parent material ITQ-29.

Aluminium control of argon solubility in silicate melts under pressure.

Understanding of the crystal chemistry of the Earth's deep mantle has evolved rapidly recently with the gradual acceptance of the importance of the effect of minor elements such as aluminium on the properties of major phases such as perovskite. In the early Earth, during its formation and segregation into rocky mantle and iron-rich core, it is likely that silicate liquids played a large part in the transport of volatiles to or from the deep interior. The importance of aluminium on solubility mechanisms at high pressure has so far received little attention, even though aluminium has long been recognized as exerting strong control on liquid structures at ambient conditions. Here we present constraints on the solubility of argon in aluminosilicate melt compositions up to 25 GPa and 3,000 K, using a laser-heated diamond-anvil cell. The argon contents reach a maximum that persists to pressures as high as 17 GPa (up to 500 km deep in an early magma ocean), well above that expected on the basis of Al-free melt experiments. A distinct drop in argon solubility observed over a narrow pressure range correlates well with the expected void loss in the melt structure predicted by recent molecular dynamics simulations. These results provide a process for noble gas sequestration in the mantle at various depths in a cooling magma ocean. The concept of shallow partial melting as a unique process for extracting noble gases from the early Earth, thereby defining the initial atmospheric abundance, may therefore be oversimplified.

Pressure-induced spin transition and site-selective metallization in CoCl2.

The interplay between spin states and metallization in compressed CoCl2 is investigated by combining diffraction, resistivity and spectroscopy techniques under high-pressure conditions and ab-initio calculations. A pressure-induced metallization along with a Co2+ high-spin (S = 3/2) to low-spin (S = 1/2) crossover transition is observed at high pressure near 70 GPa. This metallization process, which is associated with the p-d charge-transfer band gap closure, maintains the localization of 3d electrons around Co2+, demonstrating that metallization and localized Co2+ -3d low-spin magnetism can coexist prior to the full 3d-electron delocalization (Mott-Hubbard d-d breakdown) at pressures greater than 180 GPa.

Putting pressure on aromaticity along with in situ experimental electron density of a molecular crystal.

When pressure is applied, the molecules inside a crystal undergo significant changes of their stereoelectronic properties. The most interesting are those enhancing the reactivity of systems that would be otherwise rather inert at ambient conditions. Before a reaction can occur, however, a molecule must be activated, which means destabilized. In aromatic compounds, molecular stability originates from the resonance between two electronic configurations. Here we show how the resonance energy can be decreased in molecular crystals on application of pressure. The focus is on syn-1,6:8,13-Biscarbonyl[14]annulene, an aromatic compound at ambient conditions that gradually localizes one of the resonant configurations on compression. This phenomenon is evident from the molecular geometries measured at several pressures and from the experimentally determined electron density distribution at 7.7 GPa; the observations presented in this work are validated by periodic DFT calculations.

Partitioning experiments in the laser-heated diamond anvil cell: volatile content in the Earth's core.

The present state of the Earth evolved from energetic events that were determined early in the history of the Solar System. A key process in reconciling this state and the observable mantle composition with models of the original formation relies on understanding the planetary processing that has taken place over the past 4.5Ga. Planetary size plays a key role and ultimately determines the pressure and temperature conditions at which the materials of the early solar nebular segregated. We summarize recent developments with the laser-heated diamond anvil cell that have made possible extension of the conventional pressure limit for partitioning experiments as well as the study of volatile trace elements. In particular, we discuss liquid-liquid, metal-silicate (M-Sil) partitioning results for several elements in a synthetic chondritic mixture, spanning a wide range of atomic number-helium to iodine. We examine the role of the core as a possible host of both siderophile and trace elements and the implications that early segregation processes at deep magma ocean conditions have for current mantle signatures, both compositional and isotopic. The results provide some of the first experimental evidence that the core is the obvious replacement for the long-sought, deep mantle reservoir. If so, they also indicate the need to understand the detailed nature and scale of core-mantle exchange processes, from atomic to macroscopic, throughout the age of the Earth to the present day.

Lattice vibrations and electronic transitions in the rare-earth metals: praseodymium under pressure.

Praseodymium was investigated by Raman spectroscopy under pressure. A negative pressure shift of the E(2g) mode is observed in the dhcp phase, which indicates that the initial structural sequence hcp-->Sm-type-->dhcp-->fcc as a whole in the regular lanthanides is associated with a softening of this mode. The pressure response of the phonon modes, observed in the monoclinic and alpha-uranium phases, where 4f bonding becomes important, is characteristic for anisotropic bonding properties.

Questioning the evidence for Earth's oldest fossils.

Structures resembling remarkably preserved bacterial and cyanobacterial microfossils from about 3,465-million-year-old Apex cherts of the Warrawoona Group in Western Australia currently provide the oldest morphological evidence for life on Earth and have been taken to support an early beginning for oxygen-producing photosynthesis. Eleven species of filamentous prokaryote, distinguished by shape and geometry, have been put forward as meeting the criteria required of authentic Archaean microfossils, and contrast with other microfossils dismissed as either unreliable or unreproducible. These structures are nearly a billion years older than putative cyanobacterial biomarkers, genomic arguments for cyanobacteria, an oxygenic atmosphere and any comparably diverse suite of microfossils. Here we report new research on the type and re-collected material, involving mapping, optical and electron microscopy, digital image analysis, micro-Raman spectroscopy and other geochemical techniques. We reinterpret the purported microfossil-like structure as secondary artefacts formed from amorphous graphite within multiple generations of metalliferous hydrothermal vein chert and volcanic glass. Although there is no support for primary biological morphology, a Fischer--Tropsch-type synthesis of carbon compounds and carbon isotopic fractionation is inferred for one of the oldest known hydrothermal systems on Earth.