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Semiempirical Crystal Field Calculations for f N ‐Systems. I. Many‐Electron Formalism of Crystal Field Effect in f N ‐Configurations
Author(s) -
Mironov V. S.,
Rosov S. P.
Publication year - 1992
Publication title -
physica status solidi (b)
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.51
H-Index - 109
eISSN - 1521-3951
pISSN - 0370-1972
DOI - 10.1002/pssb.2221690219
Subject(s) - ion , electron , hamiltonian (control theory) , formalism (music) , crystal (programming language) , lanthanide , atomic physics , ab initio , coupled cluster , ab initio quantum chemistry methods , actinide , physics , chemistry , quantum mechanics , molecule , inorganic chemistry , mathematics , art , mathematical optimization , musical , computer science , visual arts , programming language
A new many‐electron crystal field formalism for the f N ‐configuration in lanthanide and actinide ions is presented. An effective crystal field Hamiltonian is obtained by projecting the original electronic Hamiltonian of an f‐cluster (f N ‐ion + ligand environment) on the subspace of [ J, M ] > functions of the f N ‐configuration of the central ion. On the basis of this formalism a semiempirical many‐electron method is developed that allows for a practical ab initio calculation of crystal field energies in f N ‐systems. The important role of many‐electron crystal field effects in f N ‐systems with significant covalent contributions is discussed.