{"title":"内空金属富勒烯 TM@C28 (TM = Sc-、Y-、La-、Ti、Zr、Hf、V+、Nb+、Ta+)的几何形状、电子结构、键合性质和稳定性策略","authors":"Dong Liu, Yuan Shui, Tao Yang","doi":"10.3390/inorganics12020040","DOIUrl":null,"url":null,"abstract":"We performed quantum chemical calculations on the geometries, electronic structures, bonding properties, and stability strategy of endohedral metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V+, Nb+, Ta+). Our calculations revealed that there are three different lowest-energy structures with C2v, C3v, and Td symmetries for TM@C28. The HOMO–LUMO gap of all these structures ranges from 1.35 eV to 2.31 eV, in which [V@C28]+ has the lowest HOMO–LUMO gap of 1.35 eV. The molecular orbitals are mainly composed of fullerene cage orbitals and slightly encapsulated metal orbitals. The bonding analysis on the metal–cage interactions reveals they are dominated by the Coulomb term ΔEelstat and the orbital interaction term ΔEorb, in which the orbital interaction term ΔEorb contributes more than the Coulomb term ΔEelstat. The addition of one or two CF3 groups to [V@C28]+ could increase the HOMO–LUMO gap and further increase the stability of [V@C28]+.","PeriodicalId":13572,"journal":{"name":"Inorganics","volume":null,"pages":null},"PeriodicalIF":3.1000,"publicationDate":"2024-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Geometries, Electronic Structures, Bonding Properties, and Stability Strategy of Endohedral Metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V+, Nb+, Ta+)\",\"authors\":\"Dong Liu, Yuan Shui, Tao Yang\",\"doi\":\"10.3390/inorganics12020040\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"We performed quantum chemical calculations on the geometries, electronic structures, bonding properties, and stability strategy of endohedral metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V+, Nb+, Ta+). Our calculations revealed that there are three different lowest-energy structures with C2v, C3v, and Td symmetries for TM@C28. The HOMO–LUMO gap of all these structures ranges from 1.35 eV to 2.31 eV, in which [V@C28]+ has the lowest HOMO–LUMO gap of 1.35 eV. The molecular orbitals are mainly composed of fullerene cage orbitals and slightly encapsulated metal orbitals. The bonding analysis on the metal–cage interactions reveals they are dominated by the Coulomb term ΔEelstat and the orbital interaction term ΔEorb, in which the orbital interaction term ΔEorb contributes more than the Coulomb term ΔEelstat. The addition of one or two CF3 groups to [V@C28]+ could increase the HOMO–LUMO gap and further increase the stability of [V@C28]+.\",\"PeriodicalId\":13572,\"journal\":{\"name\":\"Inorganics\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.1000,\"publicationDate\":\"2024-01-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.3390/inorganics12020040\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.3390/inorganics12020040","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
We performed quantum chemical calculations on the geometries, electronic structures, bonding properties, and stability strategy of endohedral metallofullerenes TM@C28 (TM = Sc−, Y−, La−, Ti, Zr, Hf, V+, Nb+, Ta+). Our calculations revealed that there are three different lowest-energy structures with C2v, C3v, and Td symmetries for TM@C28. The HOMO–LUMO gap of all these structures ranges from 1.35 eV to 2.31 eV, in which [V@C28]+ has the lowest HOMO–LUMO gap of 1.35 eV. The molecular orbitals are mainly composed of fullerene cage orbitals and slightly encapsulated metal orbitals. The bonding analysis on the metal–cage interactions reveals they are dominated by the Coulomb term ΔEelstat and the orbital interaction term ΔEorb, in which the orbital interaction term ΔEorb contributes more than the Coulomb term ΔEelstat. The addition of one or two CF3 groups to [V@C28]+ could increase the HOMO–LUMO gap and further increase the stability of [V@C28]+.
期刊介绍:
Inorganics is an open access journal that covers all aspects of inorganic chemistry research. Topics include but are not limited to: synthesis and characterization of inorganic compounds, complexes and materials structure and bonding in inorganic molecular and solid state compounds spectroscopic, magnetic, physical and chemical properties of inorganic compounds chemical reactivity, physical properties and applications of inorganic compounds and materials mechanisms of inorganic reactions organometallic compounds inorganic cluster chemistry heterogenous and homogeneous catalytic reactions promoted by inorganic compounds thermodynamics and kinetics of significant new and known inorganic compounds supramolecular systems and coordination polymers bio-inorganic chemistry and applications of inorganic compounds in biological systems and medicine environmental and sustainable energy applications of inorganic compounds and materials MD