High-Pressure Experimental and DFT Structural Studies of Aurichalcite Mineral
We report on high-pressure angle-dispersive synchrotron X-ray diffraction data of a natural Zn<sub>3.78(2)</sub>Cu<sub>1.22(2)</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>6</sub> aurichalcite mineral up to 7.6 GPa and ab initio total energy c...
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MDPI AG
2023-04-01
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| Series: | Minerals |
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| Online Access: | https://www.mdpi.com/2075-163X/13/5/619 |
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| author | David Santamaría-Pérez Raquel Chuliá-Jordán Alberto Otero-de-la-Roza Robert Oliva Catalin Popescu |
| author_facet | David Santamaría-Pérez Raquel Chuliá-Jordán Alberto Otero-de-la-Roza Robert Oliva Catalin Popescu |
| author_sort | David Santamaría-Pérez |
| collection | DOAJ |
| description | We report on high-pressure angle-dispersive synchrotron X-ray diffraction data of a natural Zn<sub>3.78(2)</sub>Cu<sub>1.22(2)</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>6</sub> aurichalcite mineral up to 7.6 GPa and ab initio total energy calculations of the aurichalcite structure with three different Zn-Cu stoichiometries (Zn:Cu ratios = 10:0, 8:2 and 6:4). A monoclinic-to-triclinic displacive second-order phase transition was found experimentally at 3 GPa. The experimental bulk modulus of the initial <i>P</i>2<sub>1</sub>/<i>m</i> aurichalcite is B<sub>0</sub> = 66(2) GPa, with a first-pressure derivative of B<sub>0</sub>′ = 9(2). A comparison with other basic copper and zinc carbonates shows that this B<sub>0</sub> value is considerably larger than those of malachite and azurite. This relative incompressibility occurs despite the fact that aurichalcite features a layered structure due to the number of directed hydrogen bonds between carbonate groups and the cation-centered oxygen polyhedra forming complex sheets. The existence of different bond types and polyhedral compressibilities entails a certain anisotropic compression, with axial compressibilities <i>κ<sub>a</sub></i><sub>0</sub> = 3.79(5)·10<sup>−3</sup> GPa<sup>−1</sup>, <i>κ<sub>b</sub></i><sub>0</sub> = 5.44(9)·10<sup>−3</sup> GPa<sup>−1</sup> and <i>κ<sub>c</sub></i><sub>0</sub> = 4.61(9)·10<sup>−3</sup> GPa<sup>−1</sup>. Additional density-functional theory calculations on the <i>C</i>2/<i>m</i> hydrozincite-type structure with different Zn:Cu compositional ratios shows that the aurichalcite structure is energetically more stable than the hydrozincite one for compositions of Zn:Cu = 10:0, 8:2 and 6:4 at room pressure. The pure Zn aurichalcite phase, however, was predicted to transform into hydrozincite at 18 GPa, which suggests that the experimentally observed hydrozincite structure is a metastable phase. |
| first_indexed | 2024-03-11T03:28:21Z |
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| language | English |
| last_indexed | 2024-03-11T03:28:21Z |
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| spelling | doaj.art-5d4cf42e7e404c31aef0d78ae01148522023-11-18T02:36:11ZengMDPI AGMinerals2075-163X2023-04-0113561910.3390/min13050619High-Pressure Experimental and DFT Structural Studies of Aurichalcite MineralDavid Santamaría-Pérez0Raquel Chuliá-Jordán1Alberto Otero-de-la-Roza2Robert Oliva3Catalin Popescu4Departamento de Física Aplicada-ICMUV, MALTA Consolider Team, Universitat de Valencia, 46100 Valencia, SpainDepartamento de Didáctica de las Ciencias Experimentales y Sociales, Universitat de Valencia, 46022 Valencia, SpainDepartamento de Química Física y Analítica, Facultad de Química, Universidad de Oviedo, MALTA Consolider Team, 33006 Oviedo, SpainGEO3BCN—Geosciences Barcelona, Consejo Superior de Investigaciones Científicas (CSIC), 08028 Barcelona, SpainCELLS-ALBA Synchrotron Light Facility, Cerdanyola del Vallés, 08290 Barcelona, SpainWe report on high-pressure angle-dispersive synchrotron X-ray diffraction data of a natural Zn<sub>3.78(2)</sub>Cu<sub>1.22(2)</sub>(CO<sub>3</sub>)<sub>2</sub>(OH)<sub>6</sub> aurichalcite mineral up to 7.6 GPa and ab initio total energy calculations of the aurichalcite structure with three different Zn-Cu stoichiometries (Zn:Cu ratios = 10:0, 8:2 and 6:4). A monoclinic-to-triclinic displacive second-order phase transition was found experimentally at 3 GPa. The experimental bulk modulus of the initial <i>P</i>2<sub>1</sub>/<i>m</i> aurichalcite is B<sub>0</sub> = 66(2) GPa, with a first-pressure derivative of B<sub>0</sub>′ = 9(2). A comparison with other basic copper and zinc carbonates shows that this B<sub>0</sub> value is considerably larger than those of malachite and azurite. This relative incompressibility occurs despite the fact that aurichalcite features a layered structure due to the number of directed hydrogen bonds between carbonate groups and the cation-centered oxygen polyhedra forming complex sheets. The existence of different bond types and polyhedral compressibilities entails a certain anisotropic compression, with axial compressibilities <i>κ<sub>a</sub></i><sub>0</sub> = 3.79(5)·10<sup>−3</sup> GPa<sup>−1</sup>, <i>κ<sub>b</sub></i><sub>0</sub> = 5.44(9)·10<sup>−3</sup> GPa<sup>−1</sup> and <i>κ<sub>c</sub></i><sub>0</sub> = 4.61(9)·10<sup>−3</sup> GPa<sup>−1</sup>. Additional density-functional theory calculations on the <i>C</i>2/<i>m</i> hydrozincite-type structure with different Zn:Cu compositional ratios shows that the aurichalcite structure is energetically more stable than the hydrozincite one for compositions of Zn:Cu = 10:0, 8:2 and 6:4 at room pressure. The pure Zn aurichalcite phase, however, was predicted to transform into hydrozincite at 18 GPa, which suggests that the experimentally observed hydrozincite structure is a metastable phase.https://www.mdpi.com/2075-163X/13/5/619aurichalcite mineralbasic carbonatehigh-pressurephase transitionstructurehydrozincite |
| spellingShingle | David Santamaría-Pérez Raquel Chuliá-Jordán Alberto Otero-de-la-Roza Robert Oliva Catalin Popescu High-Pressure Experimental and DFT Structural Studies of Aurichalcite Mineral Minerals aurichalcite mineral basic carbonate high-pressure phase transition structure hydrozincite |
| title | High-Pressure Experimental and DFT Structural Studies of Aurichalcite Mineral |
| title_full | High-Pressure Experimental and DFT Structural Studies of Aurichalcite Mineral |
| title_fullStr | High-Pressure Experimental and DFT Structural Studies of Aurichalcite Mineral |
| title_full_unstemmed | High-Pressure Experimental and DFT Structural Studies of Aurichalcite Mineral |
| title_short | High-Pressure Experimental and DFT Structural Studies of Aurichalcite Mineral |
| title_sort | high pressure experimental and dft structural studies of aurichalcite mineral |
| topic | aurichalcite mineral basic carbonate high-pressure phase transition structure hydrozincite |
| url | https://www.mdpi.com/2075-163X/13/5/619 |
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