The role of radial nodes of atomic orbitals for chemical bonding and the periodic table

@article{Kaupp2007TheRO,
  title={The role of radial nodes of atomic orbitals for chemical bonding and the periodic table},
  author={Martin Kaupp},
  journal={Journal of Computational Chemistry},
  year={2007},
  volume={28}
}
  • M. Kaupp
  • Published 2007
  • Medicine, Computer Science, Chemistry
  • Journal of Computational 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… Expand
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References

SHOWING 1-10 OF 53 REFERENCES
Chemical Bonding in Higher Main Group Elements
Many concepts used for a qualitative description of chemical bonding that originated in the early days of theoretical chemistry have been vindicated recently by quantum chemical calculations, at… Expand
Analysis of nondynamical correlation in the metal–ligand bond. Pauli repulsion and orbital localization in MnO−4
The nondynamical correlation error in first row transition metal complexes is studied through calculations on the permanganate ion. The source of the error is the well‐known Hartree–Fock failure in… Expand
The challenge of the so-called electron configurations of the transition metals.
TLDR
The empirically and theoretically well-founded Rydberg (n-deltal) rule is to be preferred instead of the historical Madelung (n+l) rule with its large number of exceptions. Expand
On the lack of correlation between bond lengths, dissociation energies, and force constants: the fluorine-substituted ethane homologues ☆
Abstract Accurate ab initio coupled-cluster (CCSD) calculations have been used to evaluate systematically the E–E bond lengths, homonuclear dissociation energies, and force constants of a series of… Expand
A note on nodal structures, partial screening, and periodic trends among alkali metals and alkaline earths
The first ionization potential of Na is close to that of Li but much larger than that of K. Similar trends were noted for the electronegativities or for the calculated atomic charges in partially… Expand
A VALENCE BOND PERSPECTIVE ON THE MOLECULAR SHAPES OF SIMPLE METAL ALKYLS AND HYDRIDES
Many chemists use qualitative valence bond concepts to rationalize molecular structures and properties, particularly for main group elements. Extension of Pauling's valence bond concepts to… Expand
"Non-VSEPR" Structures and Bonding in d(0) Systems.
  • M. Kaupp
  • Medicine, Chemistry
  • Angewandte Chemie
  • 2001
TLDR
This work attempts to provide a comprehensive view, both of the types of deviations of d(0) and related complexes from regular coordination arrangements, and of the theoretical framework that allows their rationalization. Expand
Dirac-Fock One-Centre Calculations Part 8. The 1Σ States of ScH, YH, LaH, AcH, TmH, LuH and LrH
Dirac-Fock one-centre expansion calculations are reported for the title molecules. The calculated bond lengths of YH, LaH and LuH are about 5% above experiment. The calculated force constants for YH… Expand
Benchmarking approximate density functional theory. I. s/d excitation energies in 3d transition metal cations
TLDR
The results reveal that computed s/d excitation energies obtained for the individual ions depend in markedly different ways on the amount of exact exchange admixture and that there is no single optimal and transferable exchange parameter to create a hybrid functional that yields improved results for all ions alike. Expand
Orthogonal and non-orthogonal hybrids
Abstract Ab initio MO wave functions for XHn molecules are analyzed in terms of the hybridization concept. It was found that for X from the first row (especially for carbon) the hybrid-AOs so… Expand
...
1
2
3
4
5
...