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The concept of the topological atom within the MO ‐ LCAO approach. II. On the nature of the nephelauxetic effect
Author(s) -
Proinov E.,
Neshey N.,
Andreev A.
Publication year - 1988
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560340102
Subject(s) - linear combination of atomic orbitals , atom (system on chip) , field (mathematics) , ligand field theory , chemistry , symmetry (geometry) , physics , topology (electrical circuits) , computational chemistry , electron , quantum mechanics , atomic orbital , mathematics , pure mathematics , combinatorics , ion , computer science , geometry , embedded system
A new MO ‐ LCAO description of the nephelauxetic effect is proposed based on the concept of the topological atom and on the method of reduced density matrices. This approach allows one to overcome some conceptual difficulties of ligand‐field theory and to derive effective parameters of d ‐ d electron repulsion of a bound transition‐metal in a proper way. The two ligand‐field mechanisms of the nephelauxetic effect—the central field covalency and the symmetry‐restricted covalency—are clarified and generalized. In addition, a new factor, important for the nephelauxetic effect is found: its size‐dependence on the region of the topological atom.