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Dependence of relativistic effects on electronic configuration in the neutral atoms of d‐ and f‐block elements
Author(s) -
Autschbach J.,
Siekierski S.,
Seth M.,
Schwerdtfeger P.,
Schwarz W. H. E.
Publication year - 2002
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.10060
Subject(s) - atomic physics , relativistic quantum chemistry , electron , valence (chemistry) , valence electron , physics , inverse , chemistry , population , ion , quantum mechanics , geometry , mathematics , demography , sociology
Abstract Although most neutral d‐ and f‐block atoms have n d g −2 ( n + 1)s 2 and ( n − 1)f g −2 (n + 1)s 2 ground configurations, respectively, where g is the group number (i.e., number of valence electrons), one‐third of these 63 atoms prefer a higher d‐population, namely via ( n + 1)s→nd “outer” to “inner” electron shift (particularly atoms from the second d‐row), or via ( n − 1)f→ n d “inner” to “outer” electron shift (particularly atoms from the second f‐row). Although the response to the modified self‐consistent field is orbital destabilization and expansion for ( n + 1)s→ n d, and stabilization and contraction for ( n − 1)f→ n d, the relativistic modification of the valence orbital responses is stabilization in both cases. This is explained by double perturbation theory. Accordingly, electron configuration and relativity trigger the orbital energies, the orbital populations and the chemical shell effects in different ways. The particularly pronounced relativistic effects in groups 10 and 11, the so‐called gold maximum, occur because of particularly efficient cooperative nonrelativistic shell effects and relativistic stabilization effects (inverse indirect effect) at the end of the d‐block. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 804–813, 2002