{"title":"单电子空间中镧系配合物配体场的电荷-电位模型","authors":"Oliver Waldmann*, ","doi":"10.1021/acs.inorgchem.5c0068710.1021/acs.inorgchem.5c00687","DOIUrl":null,"url":null,"abstract":"<p >The ligand field interactions in lanthanide-based magnetic molecular complexes are crucial for their magnetic properties, and simple models for rationalizing the ligand field effects are much desired. In this work, a charge-potential model is formulated in detail, which describes the ligand field interactions as an electrostatic interaction between a generalized single-electron charge density representing the 4<i>f</i> electrons and an electrostatic potential representing the ligands. The model is equivalent to a quantum mechanical effective spin Hamiltonian in the space of the electron <i>f</i> orbitals. Furthermore, the relation with the generalized many-electron charge density and familiar effective spin Hamiltonian in the space of the ground <i>J</i> multiplet is discussed. This permits us to translate the results of any model of the ligand field splittings in the <i>J</i> multiplet, which includes high-level ab initio techniques, into the single-electron domain, and vice versa. Models based on <i>f</i> orbitals are often well suited for rationalization, and it can be hoped that the results in this work will help us better understand the effects of ligand field in lanthanide complexes.</p><p >For lanthanide complexes it is shown that the ligand field interactions can generally be understood in terms of an interaction between a generalized single-electron charge density representing the <i>f</i> orbitals and an electrostatic potential representing the ligands, as alternative to the common effective spin Hamiltonian approach. Models based on <i>f</i> orbitals often allow for an easier rationalization of the ligand field interactions, and can help us to better understand the effects of ligand field.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 15","pages":"7666–7681 7666–7681"},"PeriodicalIF":4.7000,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.inorgchem.5c00687","citationCount":"0","resultStr":"{\"title\":\"Charge-Potential Model of Ligand Field in Lanthanide Complexes in the Single-Electron Space\",\"authors\":\"Oliver Waldmann*, \",\"doi\":\"10.1021/acs.inorgchem.5c0068710.1021/acs.inorgchem.5c00687\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The ligand field interactions in lanthanide-based magnetic molecular complexes are crucial for their magnetic properties, and simple models for rationalizing the ligand field effects are much desired. In this work, a charge-potential model is formulated in detail, which describes the ligand field interactions as an electrostatic interaction between a generalized single-electron charge density representing the 4<i>f</i> electrons and an electrostatic potential representing the ligands. The model is equivalent to a quantum mechanical effective spin Hamiltonian in the space of the electron <i>f</i> orbitals. Furthermore, the relation with the generalized many-electron charge density and familiar effective spin Hamiltonian in the space of the ground <i>J</i> multiplet is discussed. This permits us to translate the results of any model of the ligand field splittings in the <i>J</i> multiplet, which includes high-level ab initio techniques, into the single-electron domain, and vice versa. Models based on <i>f</i> orbitals are often well suited for rationalization, and it can be hoped that the results in this work will help us better understand the effects of ligand field in lanthanide complexes.</p><p >For lanthanide complexes it is shown that the ligand field interactions can generally be understood in terms of an interaction between a generalized single-electron charge density representing the <i>f</i> orbitals and an electrostatic potential representing the ligands, as alternative to the common effective spin Hamiltonian approach. Models based on <i>f</i> orbitals often allow for an easier rationalization of the ligand field interactions, and can help us to better understand the effects of ligand field.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 15\",\"pages\":\"7666–7681 7666–7681\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-04-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.inorgchem.5c00687\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00687\",\"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.5c00687","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-Potential Model of Ligand Field in Lanthanide Complexes in the Single-Electron Space
The ligand field interactions in lanthanide-based magnetic molecular complexes are crucial for their magnetic properties, and simple models for rationalizing the ligand field effects are much desired. In this work, a charge-potential model is formulated in detail, which describes the ligand field interactions as an electrostatic interaction between a generalized single-electron charge density representing the 4f electrons and an electrostatic potential representing the ligands. The model is equivalent to a quantum mechanical effective spin Hamiltonian in the space of the electron f orbitals. Furthermore, the relation with the generalized many-electron charge density and familiar effective spin Hamiltonian in the space of the ground J multiplet is discussed. This permits us to translate the results of any model of the ligand field splittings in the J multiplet, which includes high-level ab initio techniques, into the single-electron domain, and vice versa. Models based on f orbitals are often well suited for rationalization, and it can be hoped that the results in this work will help us better understand the effects of ligand field in lanthanide complexes.
For lanthanide complexes it is shown that the ligand field interactions can generally be understood in terms of an interaction between a generalized single-electron charge density representing the f orbitals and an electrostatic potential representing the ligands, as alternative to the common effective spin Hamiltonian approach. Models based on f orbitals often allow for an easier rationalization of the ligand field interactions, and can help us to better understand the effects of ligand field.
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.