{"title":"rh。-B12作为间隙原子的宿主:从第一性原理对B12{CN2}的一个大家族进行综述","authors":"Jean Etourneau , Samir F. Matar","doi":"10.1016/j.progsolidstchem.2020.100296","DOIUrl":null,"url":null,"abstract":"<div><p><span>Rhombohedral boron (Rh-α) considered as a matrix hosting triatomic linear interstitial elements (E) of the first period (B,C,N,O) and elements of the second period as (Si, P, S) as well as the fourth period (As), generates a relatively large family of solid state chemical systems with B</span><sub>12</sub><span>{E-E-E} generic formulation. This paper was also a good opportunity to make a short review of rh-α boron interstitial compounds. Preliminary energy calculations within quantum density functional theory DFT show enhanced cohesion versus B</span><sub>12</sub> matrix structure upon embedding the {E-E-E} providing compounds with particular physical and chemical properties. Focusing exemplarily on linear {N–C–N} cyanamide known to combine with gallium arsenide giving GaAs:CN<sub>2</sub>, as well as in forming calcium cyanamide CaCN<sub>2</sub>, the sub carbonitride B<sub>12</sub>{CN<sub>2</sub>} is proposed and studied for its electronic structure. After full unrestricted geometry optimization within B<sub>12</sub> space group R<span><math><mrow><mover><mn>3</mn><mo>‾</mo></mover></mrow></math></span>m and subsequent discussion of the cohesive energies and the energy related properties, details are provided for original electronic and magnetic structures. Particularly we show an elongated N–C–N (d<sub>C-N</sub> = 1.38 Å) versus short ones in (ionic) calcium cyanamide CaCN<sub>2</sub> (d<sub>C-N</sub> = 1.23 Å) explained by the bonding of N with one of the two B<sub>12</sub><span> boron substructures forming a “3B⋯N–C–N⋯3B “-like complex illustrated by charge density and electron localization function (ELF) and computed from the overlap population (COOP). From energy-volume equation of state<span> EOS in non spin-polarized NSP and spin polarized SP configurations the latter is found to be the ground state one, with a magnetic moment of 2 μ</span></span><sub>B</sub><span> carried by central carbon and forming a torus like magnetic charge density. Site and spin projected electronic density of states<span> DOS exhibit a small gap insulator. Furthermore, B</span></span><sub>12</sub>{CN<sub>2</sub>} is stabilized due to its magnetic character leading to a strong chemical bonding visualized by the SP COOP. The present conceptual view of B<sub>12</sub> as a host of interstitials extends the family of compounds to potential mono- and di-atomic insertions and should enhance research among the communities of solid state chemists and physicist to prepare new compounds with targeted properties.</p></div>","PeriodicalId":415,"journal":{"name":"Progress in Solid State Chemistry","volume":null,"pages":null},"PeriodicalIF":9.1000,"publicationDate":"2021-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2020.100296","citationCount":"5","resultStr":"{\"title\":\"rh.-B12 as host of interstitial atoms: Review of a large family with illustrative study of B12{CN2} from first-principles\",\"authors\":\"Jean Etourneau , Samir F. Matar\",\"doi\":\"10.1016/j.progsolidstchem.2020.100296\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p><span>Rhombohedral boron (Rh-α) considered as a matrix hosting triatomic linear interstitial elements (E) of the first period (B,C,N,O) and elements of the second period as (Si, P, S) as well as the fourth period (As), generates a relatively large family of solid state chemical systems with B</span><sub>12</sub><span>{E-E-E} generic formulation. This paper was also a good opportunity to make a short review of rh-α boron interstitial compounds. Preliminary energy calculations within quantum density functional theory DFT show enhanced cohesion versus B</span><sub>12</sub> matrix structure upon embedding the {E-E-E} providing compounds with particular physical and chemical properties. Focusing exemplarily on linear {N–C–N} cyanamide known to combine with gallium arsenide giving GaAs:CN<sub>2</sub>, as well as in forming calcium cyanamide CaCN<sub>2</sub>, the sub carbonitride B<sub>12</sub>{CN<sub>2</sub>} is proposed and studied for its electronic structure. After full unrestricted geometry optimization within B<sub>12</sub> space group R<span><math><mrow><mover><mn>3</mn><mo>‾</mo></mover></mrow></math></span>m and subsequent discussion of the cohesive energies and the energy related properties, details are provided for original electronic and magnetic structures. Particularly we show an elongated N–C–N (d<sub>C-N</sub> = 1.38 Å) versus short ones in (ionic) calcium cyanamide CaCN<sub>2</sub> (d<sub>C-N</sub> = 1.23 Å) explained by the bonding of N with one of the two B<sub>12</sub><span> boron substructures forming a “3B⋯N–C–N⋯3B “-like complex illustrated by charge density and electron localization function (ELF) and computed from the overlap population (COOP). From energy-volume equation of state<span> EOS in non spin-polarized NSP and spin polarized SP configurations the latter is found to be the ground state one, with a magnetic moment of 2 μ</span></span><sub>B</sub><span> carried by central carbon and forming a torus like magnetic charge density. Site and spin projected electronic density of states<span> DOS exhibit a small gap insulator. Furthermore, B</span></span><sub>12</sub>{CN<sub>2</sub>} is stabilized due to its magnetic character leading to a strong chemical bonding visualized by the SP COOP. The present conceptual view of B<sub>12</sub> as a host of interstitials extends the family of compounds to potential mono- and di-atomic insertions and should enhance research among the communities of solid state chemists and physicist to prepare new compounds with targeted properties.</p></div>\",\"PeriodicalId\":415,\"journal\":{\"name\":\"Progress in Solid State Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":9.1000,\"publicationDate\":\"2021-03-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/j.progsolidstchem.2020.100296\",\"citationCount\":\"5\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Progress in Solid State Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0079678620300297\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Progress in Solid State Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0079678620300297","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
rh.-B12 as host of interstitial atoms: Review of a large family with illustrative study of B12{CN2} from first-principles
Rhombohedral boron (Rh-α) considered as a matrix hosting triatomic linear interstitial elements (E) of the first period (B,C,N,O) and elements of the second period as (Si, P, S) as well as the fourth period (As), generates a relatively large family of solid state chemical systems with B12{E-E-E} generic formulation. This paper was also a good opportunity to make a short review of rh-α boron interstitial compounds. Preliminary energy calculations within quantum density functional theory DFT show enhanced cohesion versus B12 matrix structure upon embedding the {E-E-E} providing compounds with particular physical and chemical properties. Focusing exemplarily on linear {N–C–N} cyanamide known to combine with gallium arsenide giving GaAs:CN2, as well as in forming calcium cyanamide CaCN2, the sub carbonitride B12{CN2} is proposed and studied for its electronic structure. After full unrestricted geometry optimization within B12 space group Rm and subsequent discussion of the cohesive energies and the energy related properties, details are provided for original electronic and magnetic structures. Particularly we show an elongated N–C–N (dC-N = 1.38 Å) versus short ones in (ionic) calcium cyanamide CaCN2 (dC-N = 1.23 Å) explained by the bonding of N with one of the two B12 boron substructures forming a “3B⋯N–C–N⋯3B “-like complex illustrated by charge density and electron localization function (ELF) and computed from the overlap population (COOP). From energy-volume equation of state EOS in non spin-polarized NSP and spin polarized SP configurations the latter is found to be the ground state one, with a magnetic moment of 2 μB carried by central carbon and forming a torus like magnetic charge density. Site and spin projected electronic density of states DOS exhibit a small gap insulator. Furthermore, B12{CN2} is stabilized due to its magnetic character leading to a strong chemical bonding visualized by the SP COOP. The present conceptual view of B12 as a host of interstitials extends the family of compounds to potential mono- and di-atomic insertions and should enhance research among the communities of solid state chemists and physicist to prepare new compounds with targeted properties.
期刊介绍:
Progress in Solid State Chemistry offers critical reviews and specialized articles written by leading experts in the field, providing a comprehensive view of solid-state chemistry. It addresses the challenge of dispersed literature by offering up-to-date assessments of research progress and recent developments. Emphasis is placed on the relationship between physical properties and structural chemistry, particularly imperfections like vacancies and dislocations. The reviews published in Progress in Solid State Chemistry emphasize critical evaluation of the field, along with indications of current problems and future directions. Papers are not intended to be bibliographic in nature but rather to inform a broad range of readers in an inherently multidisciplinary field by providing expert treatises oriented both towards specialists in different areas of the solid state and towards nonspecialists. The authorship is international, and the subject matter will be of interest to chemists, materials scientists, physicists, metallurgists, crystallographers, ceramists, and engineers interested in the solid state.