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一维钒氧基氢化物 SrVOH 和 SrVOH 中的压力诱导转变,以及与二维 SrVOH 的比较。

Pressure-Induced Transitions in the 1-Dimensional Vanadium Oxyhydrides SrVOH and SrVOH, and Comparison to 2-Dimensional SrVOH.

机构信息

Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering , Kyoto University , Kyoto 615-8510 , Japan.

Laboratory for Materials and Structures , Tokyo Institute of Technology , Yokohama , Kanagawa 226-8503 , Japan.

出版信息

Inorg Chem. 2019 Nov 18;58(22):15393-15400. doi: 10.1021/acs.inorgchem.9b02459. Epub 2019 Oct 28.

Abstract

High-pressure X-ray diffraction measurements on the layered oxyhydrides SrVOH and SrVOH reveal that both compounds undergo a pressure-induced rock-salt to CsCl (1-2) structural transition, similar to those observed in binary compounds (oxides, halides, chalcogenides, etc.). This structural transition, observed at 43 and 45 GPa in SrVOH and SrVOH, respectively, relieves almost all of the accumulated strain on the infinite V-O-V ladders, such that the V-O bond lengths are almost identical at 0 and 50 GPa but are substantially compressed at intermediate pressures. The resistances of both materials with 1-dimensional VO ladders decrease with increasing pressure, but unlike SrVOH that contains 2-dimensional VO sheets, they remain insulating even at the highest accessible pressures. The reduction in dimensionality from planar to linear VO networks reduces the dispersion of the V-O π bands that define the band gap and leads to insulating behavior at all measured pressures.

摘要

高压 X 射线衍射测量表明,层状氢氧化物 SrVOH 和 SrVOH 都经历了一个压力诱导的岩盐到 CsCl(1-2)结构转变,类似于二元化合物(氧化物、卤化物、硫族化物等)中观察到的转变。这种结构转变分别在 SrVOH 和 SrVOH 中于 43 和 45 GPa 处观察到,几乎消除了无限 V-O-V 梯级上积累的应变,使得 V-O 键长在 0 和 50 GPa 时几乎相同,但在中间压力下会被大幅压缩。具有一维 VO 梯级的两种材料的电阻随着压力的增加而减小,但与包含二维 VO 片层的 SrVOH 不同,即使在最高可达压力下,它们仍然保持绝缘。从平面到线性 VO 网络的维度降低减少了定义带隙的 V-Oπ 带的离域,导致在所有测量的压力下都表现出绝缘行为。

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