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The infrared spectra of synthetic corundum (α-Al2O3) samples either doped directly with divalent cations (Mg2+) or containing divalent cations formed by reduction of trivalent cations in H2 gas (Co2+, Ni2+) may display broad OH stretching bands at ∼3000 cm−1 due to the structural incorporation of trace amounts of hydrogen. Experimental spectra recorded from some natural sapphires display a similar absorption band associated with a dominant absorption at 3161 cm−1, and some beryllium-diffused corundum crystals show a band at 3060 cm−1. All of these also display smaller and generally narrower bands between 1900 and 2700 cm−1, whose natures are poorly defined. In this work, the atomic-scale structure, relative stability and infrared spectroscopic properties of a series of OH defects in corundum (α-Al2O3) are theoretically investigated at the density-functional-theory level. The investigated defects consist of interstitial H+ ions forming OH groups and compensating for the charge imbalance related to the presence of divalent cations (Be2+, Mg2+, Cr2+, Mn2+, Fe2+, Co2+, Ni2+) substituted for Al3+ at nearby octahedral sites. Bands occurring at ∼3000 cm−1 in experimental spectra are assigned to the OH stretching modes of some of these defects, with bands observed around 1900 and 2700 cm−1 being assigned to overtones of corresponding OH bending modes. The results also support the assignment of the so-called “3161 cm−1 series”, observed in experimental spectra of some rubies and yellow sapphires, to structural OH groups in association with Fe2+ ions, rather than Si4+, as has been previously proposed. These inferences are also supported by analysis of correlations between band areas in experimental infrared spectra extracted from a database of corundum gemstones. A qualitative explanation relating the anomalous intensity and the polarisation properties of the OH bending overtone bands to the electrical anharmonicity of OH groups involved in medium-strength H bonds is proposed.

Single crystals of synthetic Cr-doped forsterite (Cr:Mg2SiO4) containing both Cr3+ and Cr4+ were partially hydroxylated in piston-cylinder apparatuses at 750–1300 ∘C and pressures from 0.5 to 2.5 GPa, with p(H2O) ≈Ptotal. The oxygen fugacity (fO2) was buffered by graphite-water, Ni–NiO, Re–ReO2, Fe2O3–Fe3O4 or Ag–Ag2O, and the silica activity (aSiO2) was buffered by powdered forsterite plus either enstatite (Mg2Si2O6), periclase (MgO) or zircon–baddeleyite (ZrSiO4–ZrO2). Profiles of OH content versus distance from the crystal edge were determined using Fourier transform infrared (FTIR) spectroscopy, and profiles of the oxidation state and coordination geometry of Cr were obtained, at the same positions, using K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The techniques are complementary – FTIR spectroscopy images the concentration and nature of O–H bonds, where Cr K-edge XANES spectroscopy shows the effect of the added H on the speciation of Cr already present in the lattice. Profiles of defect-specific absorbance derived from FTIR spectra were fitted to solutions of Fick's second law to derive diffusion coefficients, which yield the Arrhenius relationship for H diffusion in forsterite: log⁡10D̃[001]=-2.5±0.6+-(224±12+4.0±2.0P)2.303RT, where D̃ is the measured diffusion coefficient in m2 s−1, valid for diffusion parallel to [001] and calibrated between 1000 and 750 ∘C, P and T are in GPa and K, and R is 0.008314 kJK−1 mol−1. Diffusivity parallel to [100] is around 1 order of magnitude lower. This is consistent with previous determinations of H diffusion associated with M-site vacancies. The FTIR spectra represent a variety of Cr-bearing hydrous defects, along with defects associated with the pure Mg–Si–O–H system. It is proposed that all of the defects can form by interaction between the dry lattice, including Cr3+ and Cr4+, and fully hydroxylated M-site vacancies. The initial diffusive wave of hydroxylation is associated with neither reduction nor oxidation of Cr but with Cr4+ changing from tetrahedral to octahedral coordination. Superimposed on the H diffusion and concomitant change in Cr4+ site occupancy, but at a slower rate, producing shorter profiles, is reduction of Cr4+ to Cr3+ and potentially of Cr4+ and Cr3+ to Cr2+. In addition, by comparing FTIR data to trace element contents measured by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), constraints can be placed on absorption coefficients used for converting absorbance to H2O contents – our data support either wavenumber- or defect-dependent values of absorption coefficients. We estimate absorption coefficients of between 60 200 and 68 200 L mol−1 cm−1 for OH− associated with octahedral Cr3+ and an M-site vacancy and 18 700 to 24 900 L mol−1 cm−1 for two OH− associated with octahedrally coordinated Cr4+ and a Si vacancy (i.e. a “clinohumite-type” point defect).

The infrared spectra of natural quartz, and synthetic quartz produced in conditions relevant to natural environments, generally contain some association of OH-stretching absorption bands at 3596, 3585, 3483, 3431, 3379 and 3313 cm−1, and/or a broad band at ∼ 3400 cm−1. In this study, a series of OH-bearing defects has been theoretically investigated from first principles within the density functional theory framework. The optimized structure, infrared spectroscopic properties and relative energy of defect configurations have been determined. Comparison with experimental observations enables the identification of atomic-scale configurations related to the experimentally observed OH-stretching bands. Consistent with previous interpretations, the results confirm the assignment of the bands at 3596 and 3483 cm−1 to OH defects associated with B3+ substituting for Si4+ and to OH defects associated with Li+ cations located in the structural channels, respectively. They also confirm the assignment of the bands at 3313 and 3379 cm−1 to OH associated with the Al3+-for-Si4+ substitution and, by implication, the previously given interpretation of the 3431 cm−1 band in terms of Fermi resonance. The band at 3585 cm−1 does not appear to be related to a hydrogarnet-type defect, as has been proposed previously, but potentially corresponds to isolated OH− groups bridging two Si atoms, where the charge compensation is ensured by a nonlocal mechanism.