Low-temperature infrared spectrum and atomic-scale structure of hydrous defects in diopside

Hydrous defects in diopside (CaMgSi2O6) play an important role in the water budget of the Earth's mantle. Related OH-stretching modes lead to a variety of infrared absorption bands observed in natural or experimental samples. In the present study, we report new low-temperature infrared spectra of reference natural diopside samples in the OH-stretching range. In parallel, the structure and vibrational properties of a series of OH-bearing defects in diopside are theoretically determined at the density functional theory level. The infrared spectra make it possible to resolve additional bands in the region above 3600 cm(-1) and reveal that their anharmonic behavior differs from that of the bands at lower frequency. A comparison of theoretical results with experimental data makes it possible to propose atomic-scale geometries corresponding to observed OH-stretching bands. It confirms that the bands observed at 3620-3651 cm(-1) are related to M3+ ions substituted for Si in tetrahedral sites, while the 3420 cm(-1) band is associated with the Na+ for Ca2+ substitution. In both cases, HC incorporation compensates the charge deficit due to the heterovalent substitution. The other major mechanism of water incorporation in diopside relates to the charge compensation of cationic vacancies, among which Ca vacancies play a central role. The 3357 cm(-1) band corresponds to doubly protonated Ca vacancies in pure diopside. In experimental diopside-bearing trivalent cations, the bands at 3432-3460 cm(-1) correspond to singly protonated Ca vacancies with a nearby octahedral M3+ ion, while the 3310 cm(-1) band likely involves a more remote charge compensation byM(3+) ions. More complex defects associating Ca vacancies with tetrahedral M3+ and octahedral Ti4+ ions are proposed for the bands observed between 3500 and 3600 cm(-1) in natural diopside. The Fe2+ for Mg2+ and Fe2+ C for Ca2+ substitutions are also found to affect nearby OH-bearing defects, causing a shift and broadening of OH stretching bands in chemically more complex diopside samples.