Articles | Volume 32, issue 5
https://doi.org/10.5194/ejm-32-457-2020
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/ejm-32-457-2020
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
11 Sep 2020
Research article |
| 11 Sep 2020
| 11 Sep 2020
Theoretical infrared spectra of OH defects in corundum (α-Al2O3)
Etienne Balan
CORRESPONDING AUTHOR
Sorbonne Université, CNRS, MNHN, Institut de Minéralogie, de Physique des
Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu, 75252 Paris CEDEX 05,
France
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Michael C. Jollands, Shiyun Jin, Martial Curti, Maxime Guillaumet, Keevin Béneut, Paola Giura, and Etienne Balan
Eur. J. Mineral., 35, 873–890, https://doi.org/10.5194/ejm-35-873-2023, https://doi.org/10.5194/ejm-35-873-2023, 2023
Short summary
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The infrared spectrum of hydrous defects in corundum is routinely used in gemology, but the assignment of absorption bands to specific defects remains elusive. Here, we theoretically study selected defects and compare the results with available experimental data. The main results are the assignment of the
3161 cm−1 seriesto OH groups associated with Fe2+ ions and the interpretation of bands below 2700 cm−1 in corundum containing divalent cations in terms of overtones of OH bending modes.
Etienne Balan, Guillaume Radtke, Chloé Fourdrin, Lorenzo Paulatto, Heinrich A. Horn, and Yves Fuchs
Eur. J. Mineral., 35, 105–116, https://doi.org/10.5194/ejm-35-105-2023, https://doi.org/10.5194/ejm-35-105-2023, 2023
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Assignment of OH-stretching bands to specific atomic-scale environments in tourmaline is still debated, which motivates detailed theoretical studies of their vibrational properties. We have theoretically investigated the OH-stretching spectrum of foitite, showing that specific OH bands observed in the vibrational spectra of iron-rich and Na-deficient tourmalines are affected by the magnetic configuration of iron ions and X-site vacancy ordering.
Etienne Balan, Lorenzo Paulatto, Qianyu Deng, Keevin Béneut, Maxime Guillaumet, and Benoît Baptiste
Eur. J. Mineral., 34, 627–643, https://doi.org/10.5194/ejm-34-627-2022, https://doi.org/10.5194/ejm-34-627-2022, 2022
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The near-infrared spectra of hydrous minerals involve OH stretching vibrations, but their interpretation is not straightforward due to anharmonicity and vibrational coupling. We analyze the spectra of well-ordered samples of talc, brucite and lizardite to better assess the various factors contributing to the absorption bands. The results clarify the relations between the overtone spectra and their fundamental counterparts and provide a sound interpretation of the two-phonon combination bands.
Yves Fuchs, Chloé Fourdrin, and Etienne Balan
Eur. J. Mineral., 34, 239–251, https://doi.org/10.5194/ejm-34-239-2022, https://doi.org/10.5194/ejm-34-239-2022, 2022
Short summary
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Information about the local structure of tourmaline-group minerals can be obtained from the characteristic OH stretching bands in their vibrational spectra. However, their assignment to specific atomic-scale environments is debated. We address this question theoretically by investigating a series of dravite models. Our results support a local role of cationic occupancies in determining the OH stretching frequencies and bring constraints for the interpretation of the vibrational spectra.
Emmanuel Fritsch, Etienne Balan, Sabine Petit, and Farid Juillot
Eur. J. Mineral., 33, 743–763, https://doi.org/10.5194/ejm-33-743-2021, https://doi.org/10.5194/ejm-33-743-2021, 2021
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The study presents and discusses mid- and near-infrared spectra of three Mg–Ni mineral series (serpentine-like and talc-like minerals, sepiolite) commonly found in reactivated faults and sequences of clay infillings of the New Caledonian Ni-silicate deposits. This spectroscopic study sheds light on the nature of the residual mineral phases found in the clay infillings (serpentine-like minerals) and reveals the aptitude of the newly formed minerals (talc-like minerals and sepiolite) to store Ni.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, Fabien Baron, and Sabine Petit
Eur. J. Mineral., 33, 647–657, https://doi.org/10.5194/ejm-33-647-2021, https://doi.org/10.5194/ejm-33-647-2021, 2021
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Interpretation of vibrational spectra of serpentines is complexified by the common occurrence of divalent and trivalent cationic impurities at tetrahedral and octahedral sites. We theoretically investigate the effect of Fe and Al on the vibrational properties of lizardite, focusing on the OH stretching modes. The results allow us to disentangle the specific effects related to the valence and coordination states of the impurities, supporting a detailed interpretation of the experimental spectra.
Emmanuel Fritsch, Etienne Balan, Sabine Petit, and Farid Juillot
Eur. J. Mineral., 33, 447–462, https://doi.org/10.5194/ejm-33-447-2021, https://doi.org/10.5194/ejm-33-447-2021, 2021
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The study provides new insights into the OH stretching vibrations of serpentine species (lizardite, chrysotile, antigorite) encountered in veins of peridotite. A combination of infrared spectroscopy in the mid-infrared and near-infrared ranges and Raman spectroscopy enabled us to interpret most of the observed bands in the fundamental and first overtone regions of the spectra and to propose consistent spectral decomposition and assignment of the OH stretching bands for the serpentine species.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, and Sabine Petit
Eur. J. Mineral., 33, 389–400, https://doi.org/10.5194/ejm-33-389-2021, https://doi.org/10.5194/ejm-33-389-2021, 2021
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The infrared absorption spectrum of an antigorite sample, an important serpentine-group mineral, is compared to its theoretical counterpart computed at the density functional level. The model reproduces most of the observed bands, supporting their assignment to specific vibrational modes. The results provide robust interpretations of the significant differences observed between the antigorite spectrum and that of lizardite, the more symmetric serpentine variety.
Etienne Balan, Emmanuel Fritsch, Farid Juillot, Thierry Allard, and Sabine Petit
Eur. J. Mineral., 33, 209–220, https://doi.org/10.5194/ejm-33-209-2021, https://doi.org/10.5194/ejm-33-209-2021, 2021
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The OH overtone bands of kaolinite- and serpentine-group minerals observed in their near-infrared (NIR) spectra are widely used but their relation to stretching modes involving coupled OH groups is uncertain. Here, we map a molecular model of harmonically coupled anharmonic oscillators on the spectroscopic properties of 1:1 phyllosilicates. This makes it possible to interpret most of the observed bands and support the assignment of some of them to cationic substitutions in serpentines.
Etienne Balan, Lorenzo Paulatto, Jia Liu, and Jannick Ingrin
Eur. J. Mineral., 32, 505–520, https://doi.org/10.5194/ejm-32-505-2020, https://doi.org/10.5194/ejm-32-505-2020, 2020
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The atomic-scale geometry of hydrous defects in diopside is still imperfectly known despite their contribution to the Earth's water cycle. Their OH-stretching vibrations lead to a variety of infrared absorption bands. Low-temperature infrared spectroscopy makes it possible to resolve additional bands in the spectra of gem-quality natural samples. Theoretical results obtained at the density functional theory level support the assignment of the observed bands to specific atomic-scale models.
Michael C. Jollands, Marc Blanchard, and Etienne Balan
Eur. J. Mineral., 32, 311–323, https://doi.org/10.5194/ejm-32-311-2020, https://doi.org/10.5194/ejm-32-311-2020, 2020
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Quartz is a very common form of almost pure silica. It can contain a small concentration of hydrogen-bearing defects whose nature is still debated. Here, we use a theoretical approach to unravel the atomic-scale geometry of these defects. Our findings help explain some important quartz properties.
Michael C. Jollands, Shiyun Jin, Martial Curti, Maxime Guillaumet, Keevin Béneut, Paola Giura, and Etienne Balan
Eur. J. Mineral., 35, 873–890, https://doi.org/10.5194/ejm-35-873-2023, https://doi.org/10.5194/ejm-35-873-2023, 2023
Short summary
Short summary
The infrared spectrum of hydrous defects in corundum is routinely used in gemology, but the assignment of absorption bands to specific defects remains elusive. Here, we theoretically study selected defects and compare the results with available experimental data. The main results are the assignment of the
3161 cm−1 seriesto OH groups associated with Fe2+ ions and the interpretation of bands below 2700 cm−1 in corundum containing divalent cations in terms of overtones of OH bending modes.
Etienne Balan, Guillaume Radtke, Chloé Fourdrin, Lorenzo Paulatto, Heinrich A. Horn, and Yves Fuchs
Eur. J. Mineral., 35, 105–116, https://doi.org/10.5194/ejm-35-105-2023, https://doi.org/10.5194/ejm-35-105-2023, 2023
Short summary
Short summary
Assignment of OH-stretching bands to specific atomic-scale environments in tourmaline is still debated, which motivates detailed theoretical studies of their vibrational properties. We have theoretically investigated the OH-stretching spectrum of foitite, showing that specific OH bands observed in the vibrational spectra of iron-rich and Na-deficient tourmalines are affected by the magnetic configuration of iron ions and X-site vacancy ordering.
Etienne Balan, Lorenzo Paulatto, Qianyu Deng, Keevin Béneut, Maxime Guillaumet, and Benoît Baptiste
Eur. J. Mineral., 34, 627–643, https://doi.org/10.5194/ejm-34-627-2022, https://doi.org/10.5194/ejm-34-627-2022, 2022
Short summary
Short summary
The near-infrared spectra of hydrous minerals involve OH stretching vibrations, but their interpretation is not straightforward due to anharmonicity and vibrational coupling. We analyze the spectra of well-ordered samples of talc, brucite and lizardite to better assess the various factors contributing to the absorption bands. The results clarify the relations between the overtone spectra and their fundamental counterparts and provide a sound interpretation of the two-phonon combination bands.
Yves Fuchs, Chloé Fourdrin, and Etienne Balan
Eur. J. Mineral., 34, 239–251, https://doi.org/10.5194/ejm-34-239-2022, https://doi.org/10.5194/ejm-34-239-2022, 2022
Short summary
Short summary
Information about the local structure of tourmaline-group minerals can be obtained from the characteristic OH stretching bands in their vibrational spectra. However, their assignment to specific atomic-scale environments is debated. We address this question theoretically by investigating a series of dravite models. Our results support a local role of cationic occupancies in determining the OH stretching frequencies and bring constraints for the interpretation of the vibrational spectra.
Emmanuel Fritsch, Etienne Balan, Sabine Petit, and Farid Juillot
Eur. J. Mineral., 33, 743–763, https://doi.org/10.5194/ejm-33-743-2021, https://doi.org/10.5194/ejm-33-743-2021, 2021
Short summary
Short summary
The study presents and discusses mid- and near-infrared spectra of three Mg–Ni mineral series (serpentine-like and talc-like minerals, sepiolite) commonly found in reactivated faults and sequences of clay infillings of the New Caledonian Ni-silicate deposits. This spectroscopic study sheds light on the nature of the residual mineral phases found in the clay infillings (serpentine-like minerals) and reveals the aptitude of the newly formed minerals (talc-like minerals and sepiolite) to store Ni.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, Fabien Baron, and Sabine Petit
Eur. J. Mineral., 33, 647–657, https://doi.org/10.5194/ejm-33-647-2021, https://doi.org/10.5194/ejm-33-647-2021, 2021
Short summary
Short summary
Interpretation of vibrational spectra of serpentines is complexified by the common occurrence of divalent and trivalent cationic impurities at tetrahedral and octahedral sites. We theoretically investigate the effect of Fe and Al on the vibrational properties of lizardite, focusing on the OH stretching modes. The results allow us to disentangle the specific effects related to the valence and coordination states of the impurities, supporting a detailed interpretation of the experimental spectra.
Emmanuel Fritsch, Etienne Balan, Sabine Petit, and Farid Juillot
Eur. J. Mineral., 33, 447–462, https://doi.org/10.5194/ejm-33-447-2021, https://doi.org/10.5194/ejm-33-447-2021, 2021
Short summary
Short summary
The study provides new insights into the OH stretching vibrations of serpentine species (lizardite, chrysotile, antigorite) encountered in veins of peridotite. A combination of infrared spectroscopy in the mid-infrared and near-infrared ranges and Raman spectroscopy enabled us to interpret most of the observed bands in the fundamental and first overtone regions of the spectra and to propose consistent spectral decomposition and assignment of the OH stretching bands for the serpentine species.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, and Sabine Petit
Eur. J. Mineral., 33, 389–400, https://doi.org/10.5194/ejm-33-389-2021, https://doi.org/10.5194/ejm-33-389-2021, 2021
Short summary
Short summary
The infrared absorption spectrum of an antigorite sample, an important serpentine-group mineral, is compared to its theoretical counterpart computed at the density functional level. The model reproduces most of the observed bands, supporting their assignment to specific vibrational modes. The results provide robust interpretations of the significant differences observed between the antigorite spectrum and that of lizardite, the more symmetric serpentine variety.
Etienne Balan, Emmanuel Fritsch, Farid Juillot, Thierry Allard, and Sabine Petit
Eur. J. Mineral., 33, 209–220, https://doi.org/10.5194/ejm-33-209-2021, https://doi.org/10.5194/ejm-33-209-2021, 2021
Short summary
Short summary
The OH overtone bands of kaolinite- and serpentine-group minerals observed in their near-infrared (NIR) spectra are widely used but their relation to stretching modes involving coupled OH groups is uncertain. Here, we map a molecular model of harmonically coupled anharmonic oscillators on the spectroscopic properties of 1:1 phyllosilicates. This makes it possible to interpret most of the observed bands and support the assignment of some of them to cationic substitutions in serpentines.
Etienne Balan, Lorenzo Paulatto, Jia Liu, and Jannick Ingrin
Eur. J. Mineral., 32, 505–520, https://doi.org/10.5194/ejm-32-505-2020, https://doi.org/10.5194/ejm-32-505-2020, 2020
Short summary
Short summary
The atomic-scale geometry of hydrous defects in diopside is still imperfectly known despite their contribution to the Earth's water cycle. Their OH-stretching vibrations lead to a variety of infrared absorption bands. Low-temperature infrared spectroscopy makes it possible to resolve additional bands in the spectra of gem-quality natural samples. Theoretical results obtained at the density functional theory level support the assignment of the observed bands to specific atomic-scale models.
Michael C. Jollands, Marc Blanchard, and Etienne Balan
Eur. J. Mineral., 32, 311–323, https://doi.org/10.5194/ejm-32-311-2020, https://doi.org/10.5194/ejm-32-311-2020, 2020
Short summary
Short summary
Quartz is a very common form of almost pure silica. It can contain a small concentration of hydrogen-bearing defects whose nature is still debated. Here, we use a theoretical approach to unravel the atomic-scale geometry of these defects. Our findings help explain some important quartz properties.
Related subject area
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The infrared spectrum of hydrous defects in corundum is routinely used in gemology, but the assignment of absorption bands to specific defects remains elusive. Here, we theoretically study selected defects and compare the results with available experimental data. The main results are the assignment of the
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Garnet is a high-pressure mineral that may incorporate very small amounts of water in its structure (tens to hundreds of micrograms per gram H2O). In this study, we show, based on analysis and modelling, that it can transport up to several hundred micrograms per gram of H2O at depths over 80 km in a subduction zone. The analysis of garnet from the various rock types present in a subducted slab allowed us to estimate the contribution of garnet in the deep cycling of water in the earth.
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Eur. J. Mineral., 34, 627–643, https://doi.org/10.5194/ejm-34-627-2022, https://doi.org/10.5194/ejm-34-627-2022, 2022
Short summary
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The near-infrared spectra of hydrous minerals involve OH stretching vibrations, but their interpretation is not straightforward due to anharmonicity and vibrational coupling. We analyze the spectra of well-ordered samples of talc, brucite and lizardite to better assess the various factors contributing to the absorption bands. The results clarify the relations between the overtone spectra and their fundamental counterparts and provide a sound interpretation of the two-phonon combination bands.
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Matthew S. Tarling, Matteo Demurtas, Steven A. F. Smith, Jeremy S. Rooney, Marianne Negrini, Cecilia Viti, Jasmine R. Petriglieri, and Keith C. Gordon
Eur. J. Mineral., 34, 285–300, https://doi.org/10.5194/ejm-34-285-2022, https://doi.org/10.5194/ejm-34-285-2022, 2022
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Rocks containing the serpentine mineral lizardite occur in many tectonic settings. Knowing the crystal orientation of lizardite in these rocks tells us how they deform and gives insights into their physical properties. The crystal orientation of lizardite is challenging to obtain using standard techniques. To overcome this challenge, we developed a method using Raman spectroscopy to map the crystal orientation of lizardite with minimal preparation on standard thin sections.
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Common energy dispersive methods cannot accurately analyze low concentrations of cobalt in pyrite due to the overlapping of cobalt and iron peaks. The Raman method, on the other hand, has been shown to be very sensitive to a trace amount of cobalt. In addition, it can be applied on a rough surface, does not require a vacuum chamber, and operates with a laser instead of X-rays. Thus, Raman has the potential to be used as an assaying tool for Co-bearing pyrite.
Yves Fuchs, Chloé Fourdrin, and Etienne Balan
Eur. J. Mineral., 34, 239–251, https://doi.org/10.5194/ejm-34-239-2022, https://doi.org/10.5194/ejm-34-239-2022, 2022
Short summary
Short summary
Information about the local structure of tourmaline-group minerals can be obtained from the characteristic OH stretching bands in their vibrational spectra. However, their assignment to specific atomic-scale environments is debated. We address this question theoretically by investigating a series of dravite models. Our results support a local role of cationic occupancies in determining the OH stretching frequencies and bring constraints for the interpretation of the vibrational spectra.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, Fabien Baron, and Sabine Petit
Eur. J. Mineral., 33, 647–657, https://doi.org/10.5194/ejm-33-647-2021, https://doi.org/10.5194/ejm-33-647-2021, 2021
Short summary
Short summary
Interpretation of vibrational spectra of serpentines is complexified by the common occurrence of divalent and trivalent cationic impurities at tetrahedral and octahedral sites. We theoretically investigate the effect of Fe and Al on the vibrational properties of lizardite, focusing on the OH stretching modes. The results allow us to disentangle the specific effects related to the valence and coordination states of the impurities, supporting a detailed interpretation of the experimental spectra.
Emmanuel Fritsch, Etienne Balan, Sabine Petit, and Farid Juillot
Eur. J. Mineral., 33, 447–462, https://doi.org/10.5194/ejm-33-447-2021, https://doi.org/10.5194/ejm-33-447-2021, 2021
Short summary
Short summary
The study provides new insights into the OH stretching vibrations of serpentine species (lizardite, chrysotile, antigorite) encountered in veins of peridotite. A combination of infrared spectroscopy in the mid-infrared and near-infrared ranges and Raman spectroscopy enabled us to interpret most of the observed bands in the fundamental and first overtone regions of the spectra and to propose consistent spectral decomposition and assignment of the OH stretching bands for the serpentine species.
Giancarlo Capitani, Roberto Compagnoni, Roberto Cossio, Serena Botta, and Marcello Mellini
Eur. J. Mineral., 33, 425–432, https://doi.org/10.5194/ejm-33-425-2021, https://doi.org/10.5194/ejm-33-425-2021, 2021
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Unusually large lizardite (Lz) crystals from Monte Fico serpentinites, Elba (Mellini and Viti, 1994), have allowed several subsequent studies. During a µ-Raman study of serpentine minerals (Compagnoni et al., 2021), the careful microscopic examination of this Lz showed
spongymicrostructure. TEM observations confirmed that the Lz hosts voids, filled with chrysotile and polygonal serpentine; their mutual relationships indicate that Lz grew up with a skeletal habit and fibres epitactically.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, and Sabine Petit
Eur. J. Mineral., 33, 389–400, https://doi.org/10.5194/ejm-33-389-2021, https://doi.org/10.5194/ejm-33-389-2021, 2021
Short summary
Short summary
The infrared absorption spectrum of an antigorite sample, an important serpentine-group mineral, is compared to its theoretical counterpart computed at the density functional level. The model reproduces most of the observed bands, supporting their assignment to specific vibrational modes. The results provide robust interpretations of the significant differences observed between the antigorite spectrum and that of lizardite, the more symmetric serpentine variety.
Evgeniy Nikolaevich Kozlov, Ekaterina Nikolaevna Fomina, Vladimir Nikolaevich Bocharov, Mikhail Yurievich Sidorov, Natalia Sergeevna Vlasenko, and Vladimir Vladimirovich Shilovskikh
Eur. J. Mineral., 33, 283–297, https://doi.org/10.5194/ejm-33-283-2021, https://doi.org/10.5194/ejm-33-283-2021, 2021
Short summary
Short summary
Carbonophosphates (sidorenkite, bonshtedtite, and bradleyite) with the general formula Na3MCO3PO4 (M is Mn, Fe, and Mg) are often found in inclusions of carbonatite and kimberlite minerals. This article presents the results of Raman spectroscopic study and a simple algorithm for diagnosing mineral phases of the carbonophosphate group. This work may be of interest both to researchers of carbonatites and/or kimberlites and to a wide range of specialists in the field of Raman spectroscopy.
Etienne Balan, Emmanuel Fritsch, Farid Juillot, Thierry Allard, and Sabine Petit
Eur. J. Mineral., 33, 209–220, https://doi.org/10.5194/ejm-33-209-2021, https://doi.org/10.5194/ejm-33-209-2021, 2021
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The OH overtone bands of kaolinite- and serpentine-group minerals observed in their near-infrared (NIR) spectra are widely used but their relation to stretching modes involving coupled OH groups is uncertain. Here, we map a molecular model of harmonically coupled anharmonic oscillators on the spectroscopic properties of 1:1 phyllosilicates. This makes it possible to interpret most of the observed bands and support the assignment of some of them to cationic substitutions in serpentines.
Etienne Balan, Lorenzo Paulatto, Jia Liu, and Jannick Ingrin
Eur. J. Mineral., 32, 505–520, https://doi.org/10.5194/ejm-32-505-2020, https://doi.org/10.5194/ejm-32-505-2020, 2020
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The atomic-scale geometry of hydrous defects in diopside is still imperfectly known despite their contribution to the Earth's water cycle. Their OH-stretching vibrations lead to a variety of infrared absorption bands. Low-temperature infrared spectroscopy makes it possible to resolve additional bands in the spectra of gem-quality natural samples. Theoretical results obtained at the density functional theory level support the assignment of the observed bands to specific atomic-scale models.
Nada Abdel-Hak, Bernd Wunder, Ilias Efthimiopoulos, and Monika Koch-Müller
Eur. J. Mineral., 32, 469–482, https://doi.org/10.5194/ejm-32-469-2020, https://doi.org/10.5194/ejm-32-469-2020, 2020
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The structural response of the NH4+ molecule to temperature and pressure changes is studied in ammonium phengite. The symmetry of the molecule is lowered by increasing P or decreasing T; the type and mechanism of this lowered symmetry is different in both cases. Devolatilisation (NH4+ and OH loss) of ammonium phengite is studied as well. This study confirms the wide stability range of phengite and its volatiles and thus has important implications for N and H recycling into the deep Earth.
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Short summary
Corundum is an important oxide mineral which can contain low amounts of hydrogen-bearing structural defects. These defects are observed by infrared spectroscopy, but their atomic-scale geometry is still uncertain. Here, a theoretical approach makes it possible to relate most of the observed infrared bands to specific atomic configurations, highlighting the key role of other chemical impurities and defect clustering in the high-temperature incorporation of hydrogen in corundum.
Corundum is an important oxide mineral which can contain low amounts of hydrogen-bearing...
