{"title":"键价模型作为一种前瞻性方法:铜键价过剩的硫族铜晶体结构的研究。","authors":"Yves Moëlo, Aurelian Florin Popa, Vincent Dubost","doi":"10.1107/S2052520622006138","DOIUrl":null,"url":null,"abstract":"<p><p>Bond valence analysis has been applied to various copper chalcogenides with copper valence excess, i.e. where the formal valence of copper exceeds 1. This approach always reveals a copper bond valence excess relative to the unit value, correlated to an equivalent ligand bond valence deficit. In stoichiometric chalcogenides, this corresponds to one ligand electron in excess per formula unit relative to the valence equilibrium considering only Cu<sup>I</sup>. This ligand electron in excess is 50/50 shared between all or part of the Cu-atom positions, and all or part of the ligand-atom positions. In Cu<sub>3</sub>Se<sub>2</sub>, only one of the two Cu positions is involved in this sharing. It would indicate a special type of multicentre bonding (`one-electron co-operative bonding'). Calculated and ideal structural formulae according to this bond valence distribution are presented. At the crystal structure scale, Cu-ligand bonds implying the single electron in excess form one-, two- or three-dimensional subnetworks. Bond valence distribution according to two two-dimensional subnets is detailed in covellite, CuS. This bond valence description is a formal crystal-chemical representation of the metallic conductivity of holes (mixing between Cu 3d bands and ligand p bands), according to published electronic band structures. Bond valence analysis is a useful and very simple prospective approach in the search for new compounds with targeted specific physical properties.</p>","PeriodicalId":7320,"journal":{"name":"Acta crystallographica Section B, Structural science, crystal engineering and materials","volume":null,"pages":null},"PeriodicalIF":1.3000,"publicationDate":"2022-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"The bond valence model as a prospective approach: examination of the crystal structures of copper chalcogenides with Cu bond valence excess.\",\"authors\":\"Yves Moëlo, Aurelian Florin Popa, Vincent Dubost\",\"doi\":\"10.1107/S2052520622006138\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Bond valence analysis has been applied to various copper chalcogenides with copper valence excess, i.e. where the formal valence of copper exceeds 1. This approach always reveals a copper bond valence excess relative to the unit value, correlated to an equivalent ligand bond valence deficit. In stoichiometric chalcogenides, this corresponds to one ligand electron in excess per formula unit relative to the valence equilibrium considering only Cu<sup>I</sup>. This ligand electron in excess is 50/50 shared between all or part of the Cu-atom positions, and all or part of the ligand-atom positions. In Cu<sub>3</sub>Se<sub>2</sub>, only one of the two Cu positions is involved in this sharing. It would indicate a special type of multicentre bonding (`one-electron co-operative bonding'). Calculated and ideal structural formulae according to this bond valence distribution are presented. At the crystal structure scale, Cu-ligand bonds implying the single electron in excess form one-, two- or three-dimensional subnetworks. Bond valence distribution according to two two-dimensional subnets is detailed in covellite, CuS. This bond valence description is a formal crystal-chemical representation of the metallic conductivity of holes (mixing between Cu 3d bands and ligand p bands), according to published electronic band structures. Bond valence analysis is a useful and very simple prospective approach in the search for new compounds with targeted specific physical properties.</p>\",\"PeriodicalId\":7320,\"journal\":{\"name\":\"Acta crystallographica Section B, Structural science, crystal engineering and materials\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.3000,\"publicationDate\":\"2022-08-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Acta crystallographica Section B, Structural science, crystal engineering and materials\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1107/S2052520622006138\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2022/7/12 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Acta crystallographica Section B, Structural science, crystal engineering and materials","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1107/S2052520622006138","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2022/7/12 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
The bond valence model as a prospective approach: examination of the crystal structures of copper chalcogenides with Cu bond valence excess.
Bond valence analysis has been applied to various copper chalcogenides with copper valence excess, i.e. where the formal valence of copper exceeds 1. This approach always reveals a copper bond valence excess relative to the unit value, correlated to an equivalent ligand bond valence deficit. In stoichiometric chalcogenides, this corresponds to one ligand electron in excess per formula unit relative to the valence equilibrium considering only CuI. This ligand electron in excess is 50/50 shared between all or part of the Cu-atom positions, and all or part of the ligand-atom positions. In Cu3Se2, only one of the two Cu positions is involved in this sharing. It would indicate a special type of multicentre bonding (`one-electron co-operative bonding'). Calculated and ideal structural formulae according to this bond valence distribution are presented. At the crystal structure scale, Cu-ligand bonds implying the single electron in excess form one-, two- or three-dimensional subnetworks. Bond valence distribution according to two two-dimensional subnets is detailed in covellite, CuS. This bond valence description is a formal crystal-chemical representation of the metallic conductivity of holes (mixing between Cu 3d bands and ligand p bands), according to published electronic band structures. Bond valence analysis is a useful and very simple prospective approach in the search for new compounds with targeted specific physical properties.
期刊介绍:
Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials publishes scientific articles related to the structural science of compounds and materials in the widest sense. Knowledge of the arrangements of atoms, including their temporal variations and dependencies on temperature and pressure, is often the key to understanding physical and chemical phenomena and is crucial for the design of new materials and supramolecular devices. Acta Crystallographica B is the forum for the publication of such contributions. Scientific developments based on experimental studies as well as those based on theoretical approaches, including crystal-structure prediction, structure-property relations and the use of databases of crystal structures, are published.