Alfonso Hernández-Laguna, Isaac Vidal-Daza, Antonio Sánchez-Navas, Claro Ignacio Sainz-Díaz
{"title":"2M1 phlogopite–muscovite series minerals at increasing pressure to 9 GPa. I Atomic volumes and compressibilities","authors":"Alfonso Hernández-Laguna, Isaac Vidal-Daza, Antonio Sánchez-Navas, Claro Ignacio Sainz-Díaz","doi":"10.1007/s00269-023-01248-3","DOIUrl":null,"url":null,"abstract":"<div><p>Muscovite (Ms) and phlogopite (Phl) series mineral is studied in the 2<i>M</i><sub>1</sub> polytype and modeled by the substitution of three Mg<sup>2+</sup> cations in the three octahedral sites of Phl [KMg<sub>3</sub>(Si<sub>3</sub>Al)O<sub>10</sub>(OH)<sub>2</sub>] by two Al<sup>3+</sup> and one vacancy, increasing the substitution up to reach the Ms [KAl<sub>2</sub>□(Si<sub>3</sub>Al)O<sub>10</sub>(OH)<sub>2</sub>]. The series was computationally examined at DFT using Quantum ESPRESSO, as a function of pressure from − 3 to 9 GPa. Crystal structure is calculated, and cell parameters, and geometry of atomic groups agree with experimental values. OH in the Mg<sup>2+</sup> octahedrons are approximately perpendicular to the (001) plane, meanwhile when they are in Al<sup>3+</sup>, octahedral groups are approximately parallel to this plane. From Quantum Theory of Atoms in Molecules, the atomic basins are calculated as a function of the pressure, K<sup>+</sup> and basal O show the largest volumes. The bulk excess volume (Vxs) and the excess atomic volumes are analyzed as a function of the composition and the pressure. K<sup>+</sup>, basal and apical O Vxs show a behavior similar to the bulk Vxs as a function of the composition, keeping qualitatively this behavior as a function of pressure; substituent atoms do not show a Vxs behavior similar to the bulk and their effect consequently is mostly translated to atoms in the interlayer space. Atomic compressibilities are also calculated. Atomic compressibilities are separated in the different sheets of the crystal cell. Atomic moduli of K and basal O are the lowest and the ones behaving as the bulk modulus of the series. The atomic bulk modulus of the H’s is different depending of their position with respect to the (001) plane.</p></div>","PeriodicalId":20132,"journal":{"name":"Physics and Chemistry of Minerals","volume":null,"pages":null},"PeriodicalIF":1.2000,"publicationDate":"2023-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s00269-023-01248-3.pdf","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physics and Chemistry of Minerals","FirstCategoryId":"89","ListUrlMain":"https://link.springer.com/article/10.1007/s00269-023-01248-3","RegionNum":4,"RegionCategory":"地球科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Muscovite (Ms) and phlogopite (Phl) series mineral is studied in the 2M1 polytype and modeled by the substitution of three Mg2+ cations in the three octahedral sites of Phl [KMg3(Si3Al)O10(OH)2] by two Al3+ and one vacancy, increasing the substitution up to reach the Ms [KAl2□(Si3Al)O10(OH)2]. The series was computationally examined at DFT using Quantum ESPRESSO, as a function of pressure from − 3 to 9 GPa. Crystal structure is calculated, and cell parameters, and geometry of atomic groups agree with experimental values. OH in the Mg2+ octahedrons are approximately perpendicular to the (001) plane, meanwhile when they are in Al3+, octahedral groups are approximately parallel to this plane. From Quantum Theory of Atoms in Molecules, the atomic basins are calculated as a function of the pressure, K+ and basal O show the largest volumes. The bulk excess volume (Vxs) and the excess atomic volumes are analyzed as a function of the composition and the pressure. K+, basal and apical O Vxs show a behavior similar to the bulk Vxs as a function of the composition, keeping qualitatively this behavior as a function of pressure; substituent atoms do not show a Vxs behavior similar to the bulk and their effect consequently is mostly translated to atoms in the interlayer space. Atomic compressibilities are also calculated. Atomic compressibilities are separated in the different sheets of the crystal cell. Atomic moduli of K and basal O are the lowest and the ones behaving as the bulk modulus of the series. The atomic bulk modulus of the H’s is different depending of their position with respect to the (001) plane.
期刊介绍:
Physics and Chemistry of Minerals is an international journal devoted to publishing articles and short communications of physical or chemical studies on minerals or solids related to minerals. The aim of the journal is to support competent interdisciplinary work in mineralogy and physics or chemistry. Particular emphasis is placed on applications of modern techniques or new theories and models to interpret atomic structures and physical or chemical properties of minerals. Some subjects of interest are:
-Relationships between atomic structure and crystalline state (structures of various states, crystal energies, crystal growth, thermodynamic studies, phase transformations, solid solution, exsolution phenomena, etc.)
-General solid state spectroscopy (ultraviolet, visible, infrared, Raman, ESCA, luminescence, X-ray, electron paramagnetic resonance, nuclear magnetic resonance, gamma ray resonance, etc.)
-Experimental and theoretical analysis of chemical bonding in minerals (application of crystal field, molecular orbital, band theories, etc.)
-Physical properties (magnetic, mechanical, electric, optical, thermodynamic, etc.)
-Relations between thermal expansion, compressibility, elastic constants, and fundamental properties of atomic structure, particularly as applied to geophysical problems
-Electron microscopy in support of physical and chemical studies
-Computational methods in the study of the structure and properties of minerals
-Mineral surfaces (experimental methods, structure and properties)