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

IF 9.1 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Progress in Solid State Chemistry Pub Date : 2021-03-01 DOI:10.1016/j.progsolidstchem.2020.100296
Jean Etourneau , Samir F. Matar
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引用次数: 5

摘要

菱形面体硼(Rh-α)作为一种矩阵,具有第一周期(B,C,N,O)的三原子线性间隙元素(E)和第二周期元素(Si, P, S)以及第四周期元素(as),生成了相对较大的具有B12{E-E-E}通用公式的固体化学体系。本文对rh-α硼间质化合物的研究进展作了简要的综述。量子密度泛函理论DFT中的初步能量计算表明,在嵌入{E-E-E}后,相对于B12矩阵结构,内聚性增强,提供了具有特定物理和化学性质的化合物。以已知与砷化镓结合生成GaAs:CN2的线性{N-C-N}氰酰胺以及形成氰酰胺钙CaCN2为例,提出并研究了亚碳氮化物B12{CN2}的电子结构。在B12空间群R3 - m内进行了完全无限制的几何优化,并随后讨论了内聚能和与能量相关的性质,提供了原始电子和磁性结构的细节。特别是,我们显示了(离子)氰胺钙CaCN2 (dC-N = 1.38 Å)中的细长N - c -N (dC-N = 1.23 Å)与短的N (dC-N = 1.23 Å)的结合,这是由于N与两个B12硼亚结构之一形成“3B⋯N - c -N⋯3B”状复合物,由电荷密度和电子定位函数(ELF)表示,并从重叠分布(COOP)计算得出。从非自旋极化NSP态和自旋极化SP态的能量-体积方程可知,自旋极化SP态为基态,中心碳携带磁矩为2 μB,形成环面状的磁荷密度。位态和自旋投影态的电子密度表现出小间隙绝缘体。此外,B12{CN2}是稳定的,因为它的磁性导致了很强的化学键,通过SP COOP可见。目前关于B12作为大量间隙的概念观点将化合物家族扩展到潜在的单原子和双原子插入,并应加强固体化学家和物理学家之间的研究,以制备具有目标性质的新化合物。
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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 R3m 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.

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来源期刊
Progress in Solid State Chemistry
Progress in Solid State Chemistry 化学-无机化学与核化学
CiteScore
14.10
自引率
3.30%
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12
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.
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