Vera Rubin ridge (VRR) is an erosion‐resistant feature on the northwestern slope of Mount Sharp in Gale crater, Mars, and orbital visible/shortwave infrared measurements indicate it contains red hematite. The Mars Science Laboratory Curiosity rover performed an extensive campaign on VRR to study its mineralogy, geochemistry, and sedimentology to determine the depositional and diagenetic history of the ridge and constrain the processes by which the hematite could have formed. X‐ray diffraction (XRD) data from the CheMin instrument of four samples drilled on and below VRR demonstrate differences in iron, phyllosilicate, and sulfate mineralogy and hematite grain size. Hematite is common across the ridge, and its detection in a gray outcrop suggest localized regions with coarse‐grained hematite, which commonly forms from warm fluids. Broad XRD peaks for hematite in one sample below VRR and the abundance of FeOT in the amorphous component suggest the presence of nanocrystalline hematite and amorphous Fe oxides/oxyhydroxides. Well crystalline akaganeite and jarosite are present in two samples drilled from VRR, indicating at least limited alteration by acid‐saline fluids. Collapsed nontronite is present below VRR, but samples from VRR contain phyllosilicate with d(001) = 9.6 Å, possibly from ferripyrophyllite or an acid‐altered smectite. The most likely cementing agents creating the ridge are hematite and opaline silica. We hypothesize late diagenesis can explain much of the mineralogical variation on the ridge, where multiple fluid episodes with variable pH, salinity, and temperature altered the rocks, causing the precipitation and crystallization of phases that are not otherwise in equilibrium.
The contested electronic structure of [Cu(CF3)4](1-) is investigated with UV/visible/near IR spectroscopy, Cu K-edge X-ray absorption spectroscopy, and 1s2p resonant inelastic X-ray scattering. These data, supported by density functional theory, multiplet theory, and multireference calculations, support a ground state electronic configuration in which the lowest unoccupied orbital is of predominantly trifluoromethyl character. The consensus 3d(10) configuration features an inverted ligand field in which all five metal-localized molecular orbitals are located at lower energy relative to the trifluoromethyl-centered σ orbitals.
The Curiosity rover's exploration of rocks and soils in Gale crater has provided diverse geochemical and mineralogical data sets, underscoring the complex geological history of the region. We report the crystalline, clay mineral, and amorphous phase distributions of four Gale crater rocks from an 80‐m stratigraphic interval. The mineralogy of the four samples is strongly influenced by aqueous alteration processes, including variations in water chemistries, redox, pH, and temperature. Localized hydrothermal events are evidenced by gray hematite and maturation of amorphous SiO2 to opal‐CT. Low‐temperature diagenetic events are associated with fluctuating lake levels, evaporative events, and groundwater infiltration. Among all mudstones analyzed in Gale crater, the diversity in diagenetic processes is primarily captured by the mineralogy and X‐ray amorphous chemistry of the drilled rocks. Variations indicate a transition from magnetite to hematite and an increase in matrix‐associated sulfates suggesting intensifying influence from oxic, diagenetic fluids upsection. Furthermore, diagenetic fluid pathways are shown to be strongly affected by unconformities and sedimentary transitions, as evidenced by the intensity of alteration inferred from the mineralogy of sediments sampled adjacent to stratigraphic contacts.
Bimetallic (Et4N)2[Co2(L)2], (Et4N)2[1] (where (L)(3-) = (N(o-PhNC(O)(i)Pr)2)(3-)) reacts with 2 equiv of O2 to form the monometallic species (Et4N)[Co(L)O2], (Et4N)[3]. A crystallographically characterized analog (Et4N)2[Co(L)CN], (Et4N)2[2], gives insight into the structure of [3](1-). Magnetic measurements indicate [2](2-) to be an unusual high-spin Co(II)-cyano species (S = 3/2), while IR, EXAFS, and EPR spectroscopies indicate [3](1-) to be an end-on superoxide complex with an S = 1/2 ground state. By X-ray spectroscopy and calculations, [3](1-) features a high-spin Co(II) center; the net S = 1/2 spin state arises after the Co electrons couple to both the O2(•-) and the aminyl radical on redox non-innocent (L(•))(2-). Dianion [1](2-) shows both nucleophilic and electrophilic catalytic reactivity upon activation of O2 due to the presence of both a high-energy, filled O2(-) π* orbital and an empty low-lying O2(-) π* orbital in [3](1-).
Metal-to-ligand charge transfer excitations in CuI X-ray absorption spectra are introduced as spectroscopic handles for the characterization of species in homogeneous catalytic reaction mixtures. Analysis is supported by correlation of a spectral library to calculations and to complementary spectroscopic parameters.
Copper/aminoxyl species are proposed as key intermediates in aerobic alcohol oxidation. Several possible electronic structural descriptions of these species are possible, and the present study probes this issue by examining four crystallographically characterized Cu/aminoxyl halide complexes by Cu K-edge, Cu L-edge, and Cl K-edge X-ray absorption spectroscopy. The mixing coefficients between Cu, aminoxyl, and halide orbitals are determined via these techniques with support from density functional theory. The emergent electronic structure picture reveals that Cu coordination confers appreciable oxoammonium character to the aminoxyl ligand. The computational methodology is extended to one of the putative intermediates invoked in catalytic Cu/aminoxyl-driven alcohol oxidation reactions, with similar findings. Collectively, the results have important implications for the mechanism of alcohol oxidation and the underlying basis for cooperativity in this co-catalyst system.
This
paper explores the strengths and limitations of valence-to-core X-ray
emission spectroscopy (V2C XES) as a probe of coordination environments.
A library was assembled from spectra obtained for 12 diverse Cr complexes
and used to calibrate density functional theory (DFT) calculations
of V2C XES band energies. A functional dependence study was undertaken
to benchmark predictive accuracy. All 7 functionals tested reproduce
experimental V2C XES energies with an accuracy of 0.5 eV. Experimentally
calibrated, DFT calculated V2C XES spectra of 90 Cr compounds were
used to produce a quantitative spectrochemical series showing the
V2C XES band energy ranges for ligands comprising 18 distinct classes.
Substantial overlaps are detected in these ranges, which complicates
the use of V2C XES to identify ligands in the coordination spheres
of unknown Cr compounds. The ligand-dependent origins of V2C intensity
are explored for a homologous series of [CrIII(NH3)5X]2+ (X = F, Cl, Br, and I) to rationalize
the variable intensity contributions of these ligand classes.
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