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 15 January 2007
  • 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… 
View on Wiley
onlinelibrary.wiley.com
85 Citations
Background Citations
5

85 Citations

Physical origin of chemical periodicities in the system of elements
Abstract The Periodic Law, one of the great discoveries in human history, is magnificent in the art of chemistry. Different arrangements of chemical elements in differently shaped Periodic Tables…
The trend of chemisorption of hydrogen and oxygen atoms on pure transition metals: Magnetism justifies unexpected behaviour of Mn and Cr
Investigation of the distinction between van der Waals interaction and chemical bonding based on the PAEM‐MO diagram
TLDR
The potential acting on one electron in a molecule‐molecular orbital (PAEM‐MO) diagram, which draws the PAEM inserted the MO energy levels with their major atomic orbital components, is proposed and constructed and able to show clear distinction of chemical bonding from nonbonded and/or vdW interactions.
1 Chemical Bonding of Main-Group Elements
Prior to any meaningful discussion of bonding in main-group chemistry, we have to provide a reasonably accurate definition of what a main-group element is. In general, we assume that main-group…
Chemical Bonding and Bonding Models of Main-Group Compounds.
TLDR
This review examines the basis of the commonly used quantum chemical methods for calculating molecules and for analyzing their electronic structure and the bonding situation in selected representative molecules of main-group atoms is discussed.
On the Covalent vs. Charge-Shift Nature of the Metal-Metal Bond in Transition Metal Complexes: A Unified Understanding.
TLDR
These considerations create a generalized paradigm for M-M bonding in the transition-elements periods, and Pauli repulsion emerges as the factor that unifies CSB over the periods of main-group and transition elements.
Topology of the electron density of d0 transition metal compounds at subatomic resolution.
TLDR
It is demonstrated that due to the radial nodal structure of the 3d, 4d, and 5d orbitals involved in the TM-C bond formation a significant polarization of the electron density in the inner electronic shells of the TM atoms is observed and these polarizations have to be taken into account by an extended multipolar model in order to recover accurate electron density distributions from high-resolution structure factors calculated for the title compounds.
ATOMIC ORBITALS MIX BY QUANTUM MECHANICS THROUGH HYBRIDIZATION
Hybridization is defined as the concept of mixing two atomic orbitals with the same energy levels to give a degenerated new type of orbitals. This intermixing is based on quantum mechanics. The…
On the Nature of the Bonding in Coinage Metal Halides
This article analyzes the nature of the chemical bond in coinage metal halides using high-level ab initio Valence Bond (VB) theory. It is shown that these bonds display a large Charge-Shift Bonding…
On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu).
TLDR
Metal tetraoxygen molecules of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches to contribute to the general understanding of the periodic trends of oxidation states across the periodic table.
...
...

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…
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…
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.
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…
"Non-VSEPR" Structures and Bonding in d(0) Systems.
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.
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.
VALENCE BOND CONCEPTS APPLIED TO THE MOLECULAR MECHANICS DESCRIPTION OF MOLECULAR SHAPES. 3. APPLICATIONS TO TRANSITION METAL ALKYLS AND HYDRIDES
Recently we reported a qualitative, valence bond derived model for describing the shapes of transition metal complexes, with a focus on metal hydrides and alkyls. This model, based on the concepts of…
The elements of Flatland: Hartree‐Fock atomic ground states in two dimensions for Z = 1–24
The Hartree-Fock problem in two dimensions (2D) has been solved for 1 5 Z < 24 using a Gaussian basis and assuming r-’ Coulomb interactions. The order of occupation of the oneelectron states is 1s 2s…
Ab initio study of structures and stabilities of substituted lead compounds. Why is inorganic lead chemistry dominated by PbII but organolead chemistry by PbIV
The influence of electronegative substituents on the structures and relative stabilities of lead(IV) versus lead(II) species has been assessed by ab initio pseudopentential computations for a series…
SCF Relativistic Hartree–Fock Calculations on the Superheavy Elements 118–131
The energies of a number of configurations of the elements with atomic numbers 118–131 were computed by means of the relativistic Hartree–Fock method to establish the probable ground states. The…
...
...