{"title":"氧亚晶格的堆积分数:对混合热的影响","authors":"Artur Benisek, Edgar Dachs","doi":"10.1007/s00269-024-01277-6","DOIUrl":null,"url":null,"abstract":"<div><p>The heat of mixing of some petrological relevant substitutions (i.e., Mg-Al, Si-Al, Mg-Ti, Mg-Ca, and Mg-Fe) was investigated systematically in silicates, titanates, tungstates, carbonates, oxides, hydroxides, and sulphates by density functional theory calculations (e.g., melilite, chlorite, biotite, brucite, cordierite, amphibole, talc, pseudobrookite, pyroxene, olivine, wadsleyite, ilmenite, MgWO<sub>4</sub>, ringwoodite (spinel), perovskite, pyrope-grossular, magnesite-calcite, MgO-CaO, anhydrous and different hydrated MgSO<sub>4</sub>). A specific substitution is characterised by different microscopic interaction energies in different minerals, e.g., the octahedral Mg-Al exchange on a single crystallographic site in pyroxene has a microscopic interaction energy that is more than twice compared to that in biotite. A comparative investigation of the heat of mixing using microscopic interaction energies on a single crystallographic site has the advantage that they are not influenced by cation ordering. They could be successfully correlated with the stiffnesses of the minerals, which in turn were scaled to the oxygen packing fraction, a parameter that is easily available for poorly investigated minerals. With this information, the interaction energies of a certain substitution can be transferred from minerals where they are well-known to mineral groups where they are less- or unknown. Using the cross-site terms and the microscopic interaction energies, the macroscopic interaction energies of the coupled substitution, e.g., Mg + Si = Al + Al, of biotite and pyroxene were calculated, which are, however, affected by cation ordering and different degrees of local charge balance, for which appropriate models are necessary.</p></div>","PeriodicalId":20132,"journal":{"name":"Physics and Chemistry of Minerals","volume":null,"pages":null},"PeriodicalIF":1.2000,"publicationDate":"2024-06-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s00269-024-01277-6.pdf","citationCount":"0","resultStr":"{\"title\":\"The packing fraction of the oxygen sublattice: its impact on the heat of mixing\",\"authors\":\"Artur Benisek, Edgar Dachs\",\"doi\":\"10.1007/s00269-024-01277-6\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The heat of mixing of some petrological relevant substitutions (i.e., Mg-Al, Si-Al, Mg-Ti, Mg-Ca, and Mg-Fe) was investigated systematically in silicates, titanates, tungstates, carbonates, oxides, hydroxides, and sulphates by density functional theory calculations (e.g., melilite, chlorite, biotite, brucite, cordierite, amphibole, talc, pseudobrookite, pyroxene, olivine, wadsleyite, ilmenite, MgWO<sub>4</sub>, ringwoodite (spinel), perovskite, pyrope-grossular, magnesite-calcite, MgO-CaO, anhydrous and different hydrated MgSO<sub>4</sub>). A specific substitution is characterised by different microscopic interaction energies in different minerals, e.g., the octahedral Mg-Al exchange on a single crystallographic site in pyroxene has a microscopic interaction energy that is more than twice compared to that in biotite. A comparative investigation of the heat of mixing using microscopic interaction energies on a single crystallographic site has the advantage that they are not influenced by cation ordering. They could be successfully correlated with the stiffnesses of the minerals, which in turn were scaled to the oxygen packing fraction, a parameter that is easily available for poorly investigated minerals. With this information, the interaction energies of a certain substitution can be transferred from minerals where they are well-known to mineral groups where they are less- or unknown. Using the cross-site terms and the microscopic interaction energies, the macroscopic interaction energies of the coupled substitution, e.g., Mg + Si = Al + Al, of biotite and pyroxene were calculated, which are, however, affected by cation ordering and different degrees of local charge balance, for which appropriate models are necessary.</p></div>\",\"PeriodicalId\":20132,\"journal\":{\"name\":\"Physics and Chemistry of Minerals\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.2000,\"publicationDate\":\"2024-06-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s00269-024-01277-6.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/s00269-024-01277-6\",\"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}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physics and Chemistry of Minerals","FirstCategoryId":"89","ListUrlMain":"https://link.springer.com/article/10.1007/s00269-024-01277-6","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
摘要
通过密度泛函理论计算,系统地研究了硅酸盐、钛酸盐、钨酸盐、碳酸盐、氧化物、氢氧化物和硫酸盐中一些与岩石学有关的置换(即镁铝、硅铝、镁钛、镁钙和镁铁)的混合热(例如,镁铝置换、镁钛置换、镁钙置换和镁铁置换)、梅里来石、绿泥石、黑云母、白云石、堇青石、闪石、滑石、假勃洛克石、辉石、橄榄石、瓦氏石、钛铁矿、MgWO4、环钨矿(尖晶石)、透辉石、辉绿岩-毛玻璃、菱镁矿-钙钛矿、MgO-CaO、无水和不同水合硫酸镁)。特定的置换在不同矿物中具有不同的微观相互作用能,例如,辉石中单个晶体学位点上的八面体镁铝交换的微观相互作用能是黑云母的两倍多。使用单个晶体学位点上的微观相互作用能对混合热进行比较研究,其优点是不受阳离子有序性的影响。它们可以成功地与矿物的刚度相关联,而矿物的刚度又与氧堆积分数成比例,对于研究较少的矿物来说,氧堆积分数是一个很容易获得的参数。有了这些信息,就可以将某种替代物的相互作用能从已知的矿物转移到较少或未知的矿物组中。利用跨位点项和微观相互作用能,计算了耦合置换的宏观相互作用能,例如生物橄榄石和辉石中的 Mg + Si = Al + Al,但这受到阳离子有序化和不同程度的局部电荷平衡的影响,因此需要适当的模型。
The packing fraction of the oxygen sublattice: its impact on the heat of mixing
The heat of mixing of some petrological relevant substitutions (i.e., Mg-Al, Si-Al, Mg-Ti, Mg-Ca, and Mg-Fe) was investigated systematically in silicates, titanates, tungstates, carbonates, oxides, hydroxides, and sulphates by density functional theory calculations (e.g., melilite, chlorite, biotite, brucite, cordierite, amphibole, talc, pseudobrookite, pyroxene, olivine, wadsleyite, ilmenite, MgWO4, ringwoodite (spinel), perovskite, pyrope-grossular, magnesite-calcite, MgO-CaO, anhydrous and different hydrated MgSO4). A specific substitution is characterised by different microscopic interaction energies in different minerals, e.g., the octahedral Mg-Al exchange on a single crystallographic site in pyroxene has a microscopic interaction energy that is more than twice compared to that in biotite. A comparative investigation of the heat of mixing using microscopic interaction energies on a single crystallographic site has the advantage that they are not influenced by cation ordering. They could be successfully correlated with the stiffnesses of the minerals, which in turn were scaled to the oxygen packing fraction, a parameter that is easily available for poorly investigated minerals. With this information, the interaction energies of a certain substitution can be transferred from minerals where they are well-known to mineral groups where they are less- or unknown. Using the cross-site terms and the microscopic interaction energies, the macroscopic interaction energies of the coupled substitution, e.g., Mg + Si = Al + Al, of biotite and pyroxene were calculated, which are, however, affected by cation ordering and different degrees of local charge balance, for which appropriate models are necessary.
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)