4 f n−1 5 d centroid shift in lanthanides and relation with anion polarizability, covalency, and cation electronegativity
| Autor: | C.W.E. van Eijk, Pieter Dorenbos, J. Andriessen |
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| Rok vydání: | 2003 |
| Předmět: |
Quantitative Biology::Biomolecules
Nephelauxetic effect Chemistry Ab initio Configuration interaction Condensed Matter Physics Electronic Optical and Magnetic Materials Ion Inorganic Chemistry Electronegativity Condensed Matter::Materials Science Chemical bond Polarizability Computational chemistry Ab initio quantum chemistry methods Physics::Atomic and Molecular Clusters Materials Chemistry Ceramics and Composites Physical chemistry Physics::Chemical Physics Physical and Theoretical Chemistry |
| Zdroj: | Journal of Solid State Chemistry. 171:133-136 |
| ISSN: | 0022-4596 |
| DOI: | 10.1016/s0022-4596(02)00196-2 |
| Popis: | Data collected on the centroid shift of the 5 d -configuration of Ce 3+ in oxide and fluoride compounds were recently analyzed with a model involving the correlated motion between 5 d -electron and ligand electrons. The correlation effects are proportional to the polarizability of the anion ligands and it leads, like covalency, to lowering of the 5 d -orbital energies. By means of ab initio Hartree–Fock-LCAO calculations including configuration interaction the contribution from covalency and correlated motion to the centroid shift are determined separately for Ce 3+ in various compounds. It will be shown that in fluoride compounds, covalency provides an insignificant contribution. In oxides, polarizability appears to be of comparable importance as covalency. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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