The Raman spectra of pure N2, CO2, and CH4 were analyzed over the range 10 to 500 bars and from −160°C to 200°C (N2), 22°C to 350°C (CO2), and −100°C to 450°C (CH4). At constant temperature, Raman peak position, including the more intense CO2 peak (ν+), decreases (shifts to lower wave number) with increasing pressure for all three gases over the entire pressure and temperature (PT) range studied. At constant pressure, the peak position for CO2 and CH4 increases (shifts to higher wave number) with increasing temperature over the entire PT range studied. In contrast, N2 first shows an increase in peak position with increasing temperature at constant pressure, followed by a decrease in peak position with increasing temperature. The inflection temperature at which the trend reverses for N2 is located between 0°C and 50°C at pressures above ~50 bars and is pressure dependent. Below ~50 bars, the inflection temperature was observed as low as −120°C. The shifts in Raman peak positions with PT are related to relative density changes, which reflect changes in intermolecular attraction and repulsion. A conceptual model relating the Raman spectral properties of N2, CO2, and CH4 to relative density (volume) changes and attractive and repulsive forces is presented here. Additionally, reduced temperature‐dependent densimeters and barometers are presented for each pure component over the respective PT ranges. The Raman spectral behavior of the pure gases as a function of temperature and pressure is assessed to provide a framework for understanding the behavior of each component in multicomponent N2‐CO2‐CH4 gas systems in a future study.

SiO 2 is the main component of silicate melts and thus controls their network structure and physical properties. The compressibility and viscosities of melts at depth are governed by their short range atomic and electronic structure. We measured the O K-edge and the Si L 2,3 -edge in silica up to 110 GPa using X-ray Raman scattering spectroscopy, and found a striking match to calculated spectra based on structures from molecular dynamic simulations. Between 20 and 27 GPa, [4] Si species are converted into a mixture of [5] Si and [6] Si species and between 60 and 70 GPa, [6] Si becomes dominant at the expense of [5] Si with no further increase up to at least 110 GPa. Coordination higher than 6 is only reached beyond 140 GPa, corroborating results from Brillouin scattering. Network modifying elements in silicate melts may shift this change in coordination to lower pressures and thus magmas could be denser than residual solids at the depth of the core-mantle boundary.

Vibrational mode frequencies of silica species in SiO 2 -H 2 O liquids and glasses from ab initio molecular dynamics Vibrational spectroscopy techniques are commonly used to probe the atomic-scale structure of silica species in aqueous solution and hydrous silica glasses. However, unequivocal assignment of individual spectroscopic features to specific vibrational modes is challenging. In this contribution, we establish a connection between experimentally observed vibrational bands and ab initio molecular dynamics (MD) of silica species in solution and in hydrous silica glass. Using the mode-projection approach, we decompose the vibrations of silica species into subspectra resulting from several fundamental structural subunits: The SiO 4 tetrahedron of symmetry T d , the bridging oxygen (BO) Si-O-Si of symmetry C 2v , the geminal oxygen O-Si-O of symmetry C 2v , the individual Si-OH stretching and the specific ethane-like symmetric stretching contribution of the H 6 Si 2 O 7 dimer. This allows us to study relevant vibrations of these subunits in any degree of polymerization, from the Q 0 monomer up to the fully polymerized Q 4 tetrahedra. Demonstrating the potential of this approach for supplementing the interpretation of experimental spectra, we compare the calculated frequencies to those extracted from experimental Raman spectra of hydrous silica glasses and silica species in aqeous solution. We discuss observed features such as the double-peaked contribution of the Q 2 tetrahedral symmetric stretch, the individual Si-OH stretching vibrations, the origin of the experimentally observed band at 970 cm −1 and the ethane-like vibrational contribution of the H 6 Si 2 O 7 dimer at 870 cm −1 .

We measure valence-to-core x-ray emission spectra of compressed crystalline GeO 2 up to 56 GPa and of amorphous GeO 2 up to 100 GPa. In a novel approach, we extract the Ge coordination number and mean Ge-O distances from the emission energy and the intensity of the Kβ 00 emission line. The spectra of high-pressure polymorphs are calculated using the Bethe-Salpeter equation. Trends observed in the experimental and calculated spectra are found to match only when utilizing an octahedral model. The results reveal persistent octahedral Ge coordination with increasing distortion, similar to the compaction mechanism in the sequence of octahedrally coordinated crystalline GeO 2 high-pressure polymorphs.