Silicate melts at the top of the transition zone and the core-mantle boundary have significant influences on the dynamics and properties of Earth's interior. MgSiO3-rich silicate melts were among the primary components of the magma ocean and thus played essential roles in the chemical differentiation of the early Earth. Diverse macroscopic properties of silicate melts in Earth's interior, such as density, viscosity, and crystal-melt partitioning, depend on their electronic and short-range local structures at high pressures and temperatures. Despite essential roles of silicate melts in many geophysical and geodynamic problems, little is known about their nature under the conditions of Earth's interior, including the densification mechanisms and the atomistic origins of the macroscopic properties at high pressures. Here, we have probed local electronic structures of MgSiO3 glass (as a precursor to Mg-silicate melts), using high-pressure x-ray Raman spectroscopy up to 39 GPa, in which high-pressure oxygen K-edge features suggest the formation of tricluster oxygens (oxygen coordinated with three Si frameworks; 1310) between 12 and 20 GPa. Our results indicate that the densification in MgSiO3 melt is thus likely to be accompanied with the formation of triculster, in addition to a reduction in nonbridging oxygens. The pressure-induced increase in the fraction of oxygen triclusters >20 GPa would result in enhanced density, viscosity, and crystal-melt partitioning, and reduced element diffusivity in the MgSiO3 melt toward deeper part of the Earth's lower mantle.

High-resolution x-ray-absorption (XAS) experiments in the partial fluorescence yield mode (PFY) and resonant inelastic x-ray emission (RXES) measurements were performed on the intermediate-valence compound YbAl3 under pressure of up to 38 GPa. The results of the YbAl3 PFY-XAS and RXES studies show that the valence of Yb increases smoothly from 2.75 at ambient pressure to 2.93 at 38 GPa. In situ angle-dispersive synchrotron high-pressure x-ray-diffraction experiments carried out using a diamond cell at room temperature show that the ambient pressure cubic phase is stable up to 40 GPa. The results obtained from self-interaction corrected local spin density-functional calculations to understand the pressure effect on the Yb valence and compressibility are in good agreement with the experimental results.

High-resolution x-ray-absorption (XAS) experiments in the partial fluorescence yield mode (PFY) and resonant inelastic x-ray emission (RXES) measurements were performed on the intermediate-valence compound YbAl3 under pressure of up to 38 GPa. The results of the YbAl3 PFY-XAS and RXES studies show that the valence of Yb increases smoothly from 2.75 at ambient pressure to 2.93 at 38 GPa. In situ angle-dispersive synchrotron high-pressure x-ray-diffraction experiments carried out using a diamond cell at room temperature show that the ambient pressure cubic phase is stable up to 40 GPa. The results obtained from self-interaction corrected local spin density-functional calculations to understand the pressure effect on the Yb valence and compressibility are in good agreement with the experimental results.

The detailing of the intermolecular interactions in dense solid oxygen is essential for an understanding of the rich polymorphism and remarkable properties of this element at high pressure. Synchrotron inelastic x-ray scattering measurements of oxygen K-edge excitations to 38 GPa reveal changes in electronic structure and bonding on compression of the molecular solid. The measurements show that O-2 molecules interact predominantly through the half-filled 1 pi(g)* orbital < 10 GPa. Enhanced intermolecular interactions develop because of increasing overlap of the 1 pi(g)* orbital in the low-pressure phases, leading to electron delocalization and ultimately intermolecular bonding between O-2 molecules at the transition to the E-phase. The E-phase, which consists of (O-2)(4) clusters, displays the bonding characteristics of a closed-shell system. Increasing interactions between (O-2)(4) clusters develop upon compression of the E-phase, and provide a potential mechanism for intercluster bonding in still higher-pressure phases.

We present a multitechnique approach to experimentally determine the elastic anisotropy of polycrystalline hcp Fe at high pressure. Directional phonon measurements from inelastic X-ray scattering on a sample with lattice preferred orientation at 52 GPa in a diamond anvil cell were coupled with X-ray diffraction data to determine the elastic tensor. Comparison of the results from this new method with the elasticity determined by lattice strain analysis of radial X-ray diffraction measurements showed significant differences, highlighting the importance of strength anisotropy in hcp Fe. At 52 GPa, we found that a method which combines results from inelastic scattering and pressure-volume measurements gives a shape in the velocity anisotropy close to sigmoidal (with a faster c and slower a axis) a smaller magnitude in the anisotropy and compared to velocities based on the lattice strain method which gives a bell shape velocity distribution with the fast direction between the c and a axes. We used additional results from nuclear resonant inelastic X-ray scattering to constrain errors and provide additional validation of the accuracy of our results.

We present a multitechnique approach to experimentally determine the elastic anisotropy of polycrystalline hcp Fe at high pressure. Directional phonon measurements from inelastic X-ray scattering on a sample with lattice preferred orientation at 52 GPa in a diamond anvil cell were coupled with X-ray diffraction data to determine the elastic tensor. Comparison of the results from this new method with the elasticity determined by lattice strain analysis of radial X-ray diffraction measurements showed significant differences, highlighting the importance of strength anisotropy in hcp Fe. At 52 GPa, we found that a method which combines results from inelastic scattering and pressure-volume measurements gives a shape in the velocity anisotropy close to sigmoidal (with a faster c and slower a axis) a smaller magnitude in the anisotropy and compared to velocities based on the lattice strain method which gives a bell shape velocity distribution with the fast direction between the c and a axes. We used additional results from nuclear resonant inelastic X-ray scattering to constrain errors and provide additional validation of the accuracy of our results.

Results of x-ray diffraction and nitrogen K-edge x-ray Raman scattering (XRS) investigations of the crystal and electronic structure of ionic compound Li3N across two high-pressure phase transitions [A. Lazicki , Phys. Rev. Lett. 95, 165503 (2005)] are interpreted using density-functional theory. A low-energy peak in the XRS spectrum which is observed in both low-pressure hexagonal phases of Li3N and absent in the high-pressure cubic phase is found to originate from an interlayer band similar to the important free-electron-like state present in the graphite and graphite intercalated systems, but not observed previously in ionic insulators. XRS detection of the interlayer state is made possible because of its strong hybridization with the nitrogen p bands. A pressure-induced increase in the band gap of the high-pressure cubic phase of Li3N is explained by the differing pressure dependencies of different quantum-number bands and is shown to be a feature of several low-Z closed-shell ionic materials.

Results of x-ray diffraction and nitrogen K-edge x-ray Raman scattering (XRS) investigations of the crystal and electronic structure of ionic compound Li3N across two high-pressure phase transitions [A. Lazicki , Phys. Rev. Lett. 95, 165503 (2005)] are interpreted using density-functional theory. A low-energy peak in the XRS spectrum which is observed in both low-pressure hexagonal phases of Li3N and absent in the high-pressure cubic phase is found to originate from an interlayer band similar to the important free-electron-like state present in the graphite and graphite intercalated systems, but not observed previously in ionic insulators. XRS detection of the interlayer state is made possible because of its strong hybridization with the nitrogen p bands. A pressure-induced increase in the band gap of the high-pressure cubic phase of Li3N is explained by the differing pressure dependencies of different quantum-number bands and is shown to be a feature of several low-Z closed-shell ionic materials.

The phonon density of states (DOS) and phonon entropy of B2 FeAl were determined as functions of the Fe site vacancy concentration using several scattering techniques and were computed from first principles. Measurements at elevated temperature and pressure were performed to explore volume effects, test the usefulness of the quasiharmonic (QH) approximation, and provide comparison for the first-principles calculations. The average temperature and pressure dependencies of phonons were consistent with the QH model. The decrease in specific volume associated with the introduction of vacancies causes a stiffening of the DOS that was captured well with the experimentally determined Gruumlneisen parameter. Features associated with vacancies in the DOS are not well explained by this model, however, especially in the gap between the acoustic and optic branches. First-principles calculations indicated that these modes are primarily associated with vibrations of Al atoms in the first-nearest-neighbor shell of the vacancy, with some vibration amplitude also involving the second-nearest-neighbor Fe atoms. At the vacancy concentrations of study, the phonon entropy of vacancy formation was found to be approximately -1.7k(B)/atom, about half as large and of opposite sign as the configurational entropy of vacancy formation.

The phonon density of states (DOS) and phonon entropy of B2 FeAl were determined as functions of the Fe site vacancy concentration using several scattering techniques and were computed from first principles. Measurements at elevated temperature and pressure were performed to explore volume effects, test the usefulness of the quasiharmonic (QH) approximation, and provide comparison for the first-principles calculations. The average temperature and pressure dependencies of phonons were consistent with the QH model. The decrease in specific volume associated with the introduction of vacancies causes a stiffening of the DOS that was captured well with the experimentally determined Gruumlneisen parameter. Features associated with vacancies in the DOS are not well explained by this model, however, especially in the gap between the acoustic and optic branches. First-principles calculations indicated that these modes are primarily associated with vibrations of Al atoms in the first-nearest-neighbor shell of the vacancy, with some vibration amplitude also involving the second-nearest-neighbor Fe atoms. At the vacancy concentrations of study, the phonon entropy of vacancy formation was found to be approximately -1.7k(B)/atom, about half as large and of opposite sign as the configurational entropy of vacancy formation.