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四族硫属元素化合物的奇异性质的多中心键合起源。

Metavalent Bonding Origins of Unusual Properties of Group IV Chalcogenides.

机构信息

Theoretical Sciences Unit, School of Advanced Materials, JNCASR, Jakkur, Bangalore, 560 064, INDIA.

School of Advanced Materials (SAMat) and Sheikh Saqr Laboratory, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore, 560 064, INDIA.

出版信息

Adv Mater. 2023 Feb;35(7):e2208724. doi: 10.1002/adma.202208724. Epub 2022 Dec 18.

Abstract

A distinct type of metavalent bonding (MVB) is recently proposed to explain an unusual combination of anomalous functional properties of group IV chalcogenide crystals, whose electronic mechanisms and origin remain controversial. Through theoretical analysis of evolution of bonding along continuous paths in structural and chemical composition space, emergence of MVB in rocksalt chalcogenides is demonstrated as a consequence of weakly broken symmetry of parent simple-cubic crystals of Group V metalloids. High electronic degeneracy at the nested Fermi surface of parent metal drives spontaneous breaking of its translational symmetry with structural and chemical fields, which open up a small energy gap and mediate strong coupling between conduction and valence bands making metavalent crystals highly polarizable, conductive, and sensitive to bond-lengths. Stronger symmetry-breaking structural and chemical fields, however, transform them discontinuously to covalent and ionic semiconducting states. MVB involves bonding-antibonding pairwise interactions alternating along linear chains of at least five atoms, which facilitate long-range electron transfer in response to polar fields causing unusual properties. The precise picture of MVB predicts anomalous second-order Raman scattering as an addition to set off their unusual properties, and will guide in design of new metavalent materials with improved thermoelectric, ferroelectric and nontrivial electronic topological properties.

摘要

最近提出了一种独特的多价键合(MVB)类型,以解释 IV 族硫属化物晶体异常组合的异常功能特性,其电子机制和起源仍存在争议。通过在结构和化学成分空间中沿连续路径演化的理论分析,证明了岩盐硫属化物中的 MVB 是由于 V 族类金属的母体简单立方晶体的对称性较弱而产生的。母体金属嵌套费米面的高电子简并性驱动其平移对称性与结构和化学场的自发破坏,这开辟了一个小的能隙,并介导导带和价带之间的强耦合,使多价晶体具有高极化率、导电性和对键长的敏感性。然而,更强的对称性破坏结构和化学场会将它们不连续地转变为共价和离子半导体状态。MVB 涉及沿至少五个原子的线性链交替的键合-反键合成对相互作用,这有利于在引起异常性质的极性场作用下进行长程电子转移。MVB 的精确图像预测了异常的二阶拉曼散射,作为其异常性质的补充,并将指导具有改进的热电、铁电和非平凡电子拓扑性质的新型多价材料的设计。

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