High-resolution X-ray emission spectra (XES) are presented for minerals with a variety of structures. The participation of the Si 3p orbitals in bonding is influenced by the local structure around the silicon atom. In orthosilicates the distortion of the SiO44--tetrahedron influences both peak-width and the intensity of the high-energy shoulder of the Si-Kβ spectrum. In minerals containing Si-O-Si bonds there is mixing of the Si 3s and 3p orbitals giving rise to a peak on the low-energy side of the main Si-Kβ peak. When combined with X-ray photoelectron spectra (XPS), a complete molecular orbital picture of bonding can be established.

X-ray photoelectron spectroscopy can be used to measure the ionization energies of electrons in both valence band and core orbitals. As core vacancies are the initial states for X-ray emission, a knowledge of their energies for all atoms in a mineral enables all the X-ray spectra to be placed on a common energy scale. X-ray spectra are atom specific and are governed by the dipole selection rule. Thus the individual bonding roles of the different atoms are revealed by the fine structure of valence X-ray peaks (i.e. peaks which result from electron transitions between valence band orbitals and core vacancies). The juxtaposition of such spectra enables the composition of the molecular orbitals that make up the chemical bonds of a mineral to be determined.

Examples of this approach to the direct determination of electronic structure are given for silica, forsterite, brucite, and pyrite. Multi-electron effects and developments involving anisotropic X-ray emission from single crystals are also discussed.

Recent experimental and theoretical studies provide new insight into the variety of high-pressure transformations in minerals that comprise the Earth’s deep mantle and core. Representative examples of reconstructive, displacive, electronic and magnetic transformations studied by new diamond-anvil cell techniques are examined. Despite reports for various transitions in (Mg,Fe)SiO3-perovskite, the stability field of the orthorhombic phase expands relative to magnesiowüstite + SiO2 with increasing pressure and temperature. The partitioning of Fe and Mg between Mg-rich silicate perovskite magnesiowüstite depends strongly on pressure, temperature, bulk Fe/Mg ratio, and ferric iron content. The soft-mode transition in SiO2 from the rutile- to CaCl2-type structure, originally documented by X-ray powder diffraction, Raman scattering, and first-principles theory has been explored in detail by single crystal diffraction, and transitions to higher-pressure forms have been examined. The effect of H on the transformations of various nominally anhydrous phases and transitions in dense hydrous Mg-silicates are also examined. New studies of the phase diagram of FeO include the transition to rhombohedral and higher-pressure NiAs polymorphs, and provide prototypical examples of coupled structural, electronic, and magnetic transitions. High-spin/low-spin transitions in FeO have been examined by high-resolution X-ray emission spectroscopy to 150 GPa, and the results are compared with similar studies of Fe2O3 and FeS. Finally, laser-heating studies to above 150 GPa and 2500K show that (hcp) ε-Fe has a large P-T stability field. Radial XRD measurements carried out at room temperature to 220 GPa have constrained the elasticity, rheology and sound velocities of ε-Fe at core pressures.

The valence states of Mg-Al alloys are compared to those of reference materials (pure Mg and Al metals, and intermetallics). Two methods based on X-ray emission spectroscopy are proposed to determine the phases and their proportion: first, by analyzing the Al valence spectra of the Mg-rich alloys and the Mg valence spectra of the Al-rich alloys; second, by fitting with a linear combination of the reference spectra the Al spectra of the Al-rich alloys and the Mg spectra of the Mg-rich alloys. This enables us to determine that Al and Al3Mg2 are present in the 0–43.9 wt% Al composition range and Mg and Al12Mg17 are present in the 62.5–100 wt% Al composition range. In the 43.9–62.5% Al range, the alloy is single phase and an underestimation of the Al content of the alloy can be estimated from the comparison of the bandwidth of the alloy spectrum to the bandwidths of the reference spectra.