We present stellar age distributions of the Milky Way bulge region using ages for similar to 6000 high-luminosity (log (g), metal-rich ([Fe/H] >= -0.5) bulge stars observed by the Apache Point Observatory Galactic Evolution Experiment. Ages are derived using The Cannon label-transfer method, trained on a sample of nearby luminous giants with precise parallaxes for which we obtain ages using a Bayesian isochrone-matching technique. We find that the metal-rich bulge is predominantly composed of old stars (>8 Gyr). We find evidence that the planar region of the bulge (vertical bar Z(GC)vertical bar <= 0.25 kpc) is enriched in metallicity, Z, at a faster rate (dZ/dt similar to 0.0034 Gyr(-1)) than regions farther from the plane (dZ/dt similar to 0.0013 Gyr(-1) at vertical bar Z(GC)vertical bar > 1.00 kpc). We identify a nonnegligible fraction of younger stars (age similar to 2-5 Gyr) at metallicities of +0.2 < [Fe/H] < +0.4. These stars are preferentially found in the plane (vertical bar Z(GC)vertical bar <= 0.25 kpc) and at R-cy approximate to 2-3 kpc, with kinematics that are more consistent with rotation than are the kinematics of older stars at the same metallicities. We do not measure a significant age difference between stars found inside and outside the bar. These findings show that the bulge experienced an initial starburst that was more intense close to the plane than far from the plane. Then, star formation continued at supersolar metallicities in a thin disk at 2 kpc less than or similar to R-cy less than or similar to 3 kpc until similar to 2 Gyr ago.

The interior of the Earth is an important reservoir for elements that are chemically bound in minerals, melts, and gases. Analyses of the proportions of redox-sensitive elements in ancient and contemporary natural rocks provide information on the temporal redox evolution of our planet. Natural inclusions trapped in diamonds, xenoliths, and erupted magmas provide unique windows into the redox conditions of the deep Earth, and reveal evidence for heterogeneities in the mantle's oxidation state. By examining the natural rock record, we assess how redox boundaries in the deep Earth have controlled elemental cycling and what effects these boundaries have had on the temporal and chemical evolution of oxygen fugacity in the Earth's interior and atmosphere.

Solid-state topochemical polymerization (SSTP) requires well-defined geometries and space symmetries between the starting monomers and resulting polymer, and diacetylenes are excellent precursors, reacting through a 1,4-addition mechanism. The hydrocarbon molecule 1,4-diphenyl-1,3-butadiyne (DPB) has a four-carbon chain with alternating triple/single bonds, capped on each end with a phenyl group, i.e. centrosymmetric with unsaturated pi-bonding characteristics. To fully realize its potential for photocatalytic applications, improved control over the assembly process is desirable to form well-ordered poly(diphenylbutadiyne) (PDPB). Here, it is shown that with increasing pressure, DPB undergoes a series of solid-state chemical reactions while maintaining crystalline order related to the starting monomeric structure. Quenchable PDPB compounds begin forming at ca. 5 GPa, which exhibit optically-tunable absorbance and photoluminescence that is controllable through the extent of compression. Above ca. 15 GPa, the system transforms into a nonhexagonally-packed crystalline array with mixed sp(2)/sp(3) character. These stepwise changes with compression are irreversible in nature, as observed by in situ diffraction and spectroscopic methods. For the first time, the simple SSTP synthesis route allows well-aligned DPB molecules to directly transform into a PDPB material via self-assembly solely through pressure generation within a diamond anvil cell without the traditional use of catalysts, temperature, radiation, templates, or solvents.

Recent shear wave splitting measurements from the fore-arc region of the Ryukyu subduction system show large magnitude (0.3-1.6 s) trenchparallel splitting in both local and teleseismic phases. The similarity of splitting parameters associated with shallow local-S and teleseismic phases suggests that the source of anisotropy is located in the fore-arc mantle. One explanation for this pattern of shear wave splitting involves a transition from commonly observed high-temperature olivine fabrics with flow-parallel seismically fast directions to a flow-normal B-type olivine fabric in the cold fore-arc mantle of the Ryukyu wedge. We test the B-type fabric hypothesis by comparing observed splitting parameters to those predicted from geodynamic models that incorporate olivine fabric development. The distribution of olivine fabric is calculated with high-resolution thermomechanical models of the Ryukyu subduction zone that include realistic slab geometry and an experimentally based wet olivine rheology. We conclude that B-type fabric can explain the magnitude and trench-parallel orientation of deep local-S phases that sample the core of the foreare mantle. However, our calculations show that B-type fabric alone cannot account for large magnitude trench-parallel splitting associated with teleseismic phases that sample the shallow tip of the fore-arc mantle. Alternative models for trench-parallel teleseismic splitting in the shallow tip of the fore-arc mantle involve the addition of crustal or slab anisotropy and highly anisotropic foliated antigorite serpentinite. (c) 2008 Elsevier B.V. All rights reserved.

Quantum Monte Carlo (QMC) methods are useful for studies of strongly correlated materials because they are many body in nature and use the physical Hamiltonian. Typical calculations assume as a starting point a wave function constructed from single-particle orbitals obtained from one-body methods, e.g., density functional theory. However, mean-field-derived wave functions can sometimes lead to systematic QMC biases if the meanfield result poorly describes the true ground state. Here, we study the accuracy and flexibility of QMC trial wave functions using variational and fixed-node diffusion QMC estimates of the total spin density and lattice distortion of antiferromagnetic iron oxide (FeO) in the ground state B1 crystal structure. We found that for relatively simple wave functions the predicted lattice distortion was controlled by the choice of single-particle orbitals used to construct the wave function, rather than by subsequent wave function optimization techniques within QMC. By optimizing the orbitals with QMC, we then demonstrate starting-point independence of the trial wave function with respect to the method by which the orbitals were constructed by demonstrating convergence of the energy, spin density, and predicted lattice distortion for two qualitatively different sets of orbitals. The results suggest that orbital optimization is a promising method for accurate many-body calculations of strongly correlated condensed phases.

We measure the electrical resistivity of hcp iron up to similar to 170 GPa and similar to 3000 K using a four-probe van der Pauw method coupled with homogeneous flattop laser heating in a DAC, and compute its electrical and thermal conductivity by first-principles molecular dynamics including electron-phonon and electron-electron scattering. We find that the measured resistivity of hcp iron increases almost linearly with temperature, and is consistent with our computations. The results constrain the resistivity and thermal conductivity of hcp iron to similar to 80 +/- 5 mu Omega cm and similar to 100 +/- 10 W m(-1) K-1, respectively, at conditions near the core-mantle boundary. Our results indicate an adiabatic heat flow of similar to 10 +/- 1 TW out of the core, supporting a present-day geodynamo driven by thermal and compositional convection.

Here we report on the first structural and optical high-pressure investigation of MASnBr(3) (MA = [CH3NH3](+)) and CsSnBr3 halide perovskites. A massive red shift of 0.4 eV for MASnBr(3) and 0.2 eV for CsSnBr3 is observed within 1.3 to 1.5 GPa from absorption spectroscopy, followed by a huge blue shift of 0.3 and 0.5 eV, respectively. Synchrotron powder diffraction allowed us to correlate the upturn in the optical properties trend (onset of blue shift) with structural phase transitions from cubic to orthorhombic in MASnBr(3) and from tetragonal to monoclinic for CsSnBr3. Density functional theory calculations indicate a different underlying mechanism affecting the band gap evolution with pressure, a key role of metal-halide bond lengths for CsSnBr3 and cation orientation for MASnBr(3), thus showing the impact of a different A-cation on the pressure response. Finally, the investigated phases, differently from the analogous Pb-based counterparts, are robust against amorphization showing defined diffraction up to the maximum pressure used in the experiments.

Here, multiple isotope systems are tracked simultaneously in models of mantle convection and it is show that this can provide powerful constraints on the role of oceanic crust recycling in the development of isotopic end-member compositions. The dynamical models are based on high-resolution cylindrical calculations with force-balanced plates and variable chemical density. The dynamic results span a parameter space of variable realistic excess crustal density compared to experimental estimates and convective vigor measured by plate velocities and surface heat flow. Isotope geochemistry is then modeled for the U-Th-Pb, Sm-Nd, Rb-Sr, and Re-Os isotope systems. The role of a dense crustal layer in development of a HIMU-isotope signature is confirmed. The extraction of continental crust is found to be essential for the formation of all isotope compositional end-members, including HIMU. This extraction is implemented as an ad-hoc process secondary to partial melting at mid-ocean ridges and constrained by estimated isotopic abundances in the present-day crust. Whereas previous studies generated mantle isotopic arrays that spanned DMM-HIMU, the additional isotope systems in this analysis indicate that enrichment purely from ancient oceanic crust may also generate an EM-I component without invoking the subduction of sediment. In this case, the EM-I signature may be indicative of mantle enriched by oceanic crust produced before 2.25 Byr, while the HIM signature indicates enrichment by oceanic crust extracted more recently. However, it is found to be difficult to maintain a true DMM isotopic end member in Sr-Nd isotope space when significantly enriched end-members are present. This may highlight the sensitivity of the Rb-Sr system to mass exchange between the upper and lower mantle. (C) 2008 Elsevier B.V. All rights reserved.

To improve our understanding of the Earth's global carbon cycle, it is critical to characterize the distribution and storage mechanisms of carbon in silicate melts. Presently, the carbon budget of the deep Earth is not well constrained and is highly model-dependent. In silicate melts of the uppermost mantle, carbon exists predominantly as molecular carbon dioxide and carbonate, whereas at greater depths, carbon forms complex polymerized species. The concentration and speciation of carbon in silicate melts is intimately linked to the melt's composition and affects its physical and dynamic properties. Here we review the results of experiments and calculations on the solubility and speciation of carbon in silicate melts as a function of pressure, temperature, composition, polymerization, water concentration, and oxygen fugacity.