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The role of radial nodes of atomic orbitals for chemical bonding and the periodic table
Author(s) -
Kaupp Martin
Publication year - 2006
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.20522
Subject(s) - atomic orbital , electronegativity , lone pair , chemistry , chemical bond , valence (chemistry) , valence electron , orbital hybridisation , valence bond theory , chemical physics , atomic physics , electron shell , localized molecular orbitals , computational chemistry , molecular physics , electron , physics , molecule , quantum mechanics , ion , ionization , organic chemistry
The role of radial nodes, or of their absence, in valence orbitals for chemical bonding and periodic trends is discussed from a unified viewpoint. In particular, we emphasize the special role of the absence of a radial node whenever a shell with angular quantum number l is occupied for the first time (lack of “primogenic repulsion”), as with the 1s, 2p, 3d, and 4f shells. Although the consequences of the very compact 2p shell (e.g. good isovalent hybridization, multiple bonding, high electronegativity, lone‐pair repulsion, octet rule) are relatively well known, it seems that some of the aspects of the very compact 3d shell in transition‐metal chemistry are less well appreciated, e.g., the often weakened and stretched bonds at equilibrium structure, the frequently colored complexes, and the importance of nondynamical electron‐correlation effects in bonding. © 2006 Wiley Periodicals, Inc. J Comput Chem 28: 320–325, 2006