{"title":"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。","authors":"Renfeng Li, Jian Lv, Peihao Huang, Jingwei Lv, Sheng Wang, Chunhong Xu, Chao Liu* and Liangliang Li*, ","doi":"10.1021/acs.inorgchem.5c02405","DOIUrl":null,"url":null,"abstract":"<p >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 ReB<sub>2</sub>, ReB<sub>3</sub>, and ReB<sub>4</sub> 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.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 33","pages":"16923–16930"},"PeriodicalIF":4.7000,"publicationDate":"2025-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Charge Transfer Driven Bond Weakening Underlies the Inverse Boron Content-Ideal Strength Relationship in Rhenium Borides\",\"authors\":\"Renfeng Li, Jian Lv, Peihao Huang, Jingwei Lv, Sheng Wang, Chunhong Xu, Chao Liu* and Liangliang Li*, \",\"doi\":\"10.1021/acs.inorgchem.5c02405\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >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 ReB<sub>2</sub>, ReB<sub>3</sub>, and ReB<sub>4</sub> 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.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 33\",\"pages\":\"16923–16930\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-08-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02405\",\"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":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c02405","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
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.
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.