硼化铼中电荷转移驱动的键弱化是硼含量-理想强度逆关系的基础。

IF 4.7 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Renfeng Li, Jian Lv, Peihao Huang, Jingwei Lv, Sheng Wang, Chunhong Xu, Chao Liu* and Liangliang Li*, 
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引用次数: 0

摘要

硼化铼已成为超硬材料的有希望的候选者,然而,随着硼含量的变化,控制其机械性能的基本机制仍然知之甚少。通过第一性原理计算,研究了ReB2、ReB3和ReB4在多种加载条件下的理想强度和变形机制。结果表明硼化物中硼含量与硬度之间存在意想不到的反比关系,这与传统的材料设计原则相矛盾。应力-应变分析确定了以硼网络内临界B-B键断裂为特征的破坏机制。这种异常行为源于电荷重分配效应,所有化合物都表现出从Re到B的电荷转移,但硼位点的电子积累效率随着硼含量的增加而降低。这种减少的电荷转移导致基本B-B键逐渐减弱,通过晶体轨道汉密尔顿族(COHP)和Bader电荷分析定量地证明了这一点。我们强调,最佳电荷转移而不是简单的硼含量决定机械性能。这些发现为开发先进的超硬材料提供了新的指导。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Charge Transfer Driven Bond Weakening Underlies the Inverse Boron Content-Ideal Strength Relationship in Rhenium Borides

Charge Transfer Driven Bond Weakening Underlies the Inverse Boron Content-Ideal Strength Relationship in Rhenium Borides

Rhenium borides have emerged as promising candidates for superhard materials, yet the fundamental mechanisms governing their mechanical properties with varying boron content remain poorly understood. Through first-principles calculations, we investigate the ideal strength and deformation mechanisms of ReB2, ReB3, and ReB4 under multiple loading conditions. The results demonstrate an unexpected inverse relationship between boron content and hardness in rhenium borides contradicting conventional materials design principles. The stress–strain analyses identify failure mechanisms characterized by the rupture of critical B–B bonds within the boron networks. The anomalous behavior originates from charge redistribution effects, where all compounds show charge transfer from Re to B, yet the electron accumulation efficiency at boron sites diminishes with higher boron content. This reduced charge transfer leads to progressive weakening of essential B–B bonds, as quantitatively demonstrated through Crystal Orbital Hamilton Population (COHP) and Bader charge analyses. We highlight that optimal charge transfer rather than simple boron content determines mechanical performance. These findings offer new guidelines for developing advanced ultrahard materials.

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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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