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The d orbitals of second‐row elements
Author(s) -
Cruickshank D. W. J.,
Webster B. C.,
Spinnler M. A.
Publication year - 2009
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.560010628
Subject(s) - atomic orbital , molecular orbital , molecular orbital theory , chemistry , linear combination of atomic orbitals , atomic physics , localized molecular orbitals , electron configuration , molecular orbital diagram , electron , non bonding orbital , slater type orbital , orbital hybridisation , tetrahedron , computational chemistry , molecular physics , ion , physics , crystallography , molecule , quantum mechanics , organic chemistry
Atomic SCF calculations for second‐row elements with configurations involving d electrons show that under favourable conditions of spin alignment d atomic orbitals may sometimes be of a suitable size for engaging in molecular bonding. The orbital energies, however, are very small, and “simple‐minded” combination with oxygen or fluorine ligand orbitals is therefore questionable. The participation of d orbitals in bonds is possible if their energies are substantially lowered by the ligands. The Craig–Zauli electrostatic treatment of SF 6 is reconsidered and it is found that the neutral penetration integrals are large. Although this method neglects important terms, it suggests a possible mechanism for d ‐orbital participation by second‐row elements and illustrates the need for extreme caution in semiempirical MO calculations. Tetrahedral XO 4 species are also considered. Positive energies are found for d orbitals in isolated anions.