Next Article in Journal
Reconciling Experiment and Theory in the Use of Aryl-Extended Calix[4]pyrrole Receptors for the Experimental Quantification of Chloride–π Interactions in Solution
Next Article in Special Issue
Crystal Structure, Chemical Bonding and Magnetism Studies for Three Quinary Polar Intermetallic Compounds in the (Eu1−xCax)9In8(Ge1−ySny)8 (x = 0.66, y = 0.03) and the (Eu1−xCax)3In(Ge3−ySn1+y) (x = 0.66, 0.68; y = 0.13, 0.27) Phases
Previous Article in Journal
Undetected Toxicity Risk in Pharmacogenetic Testing for Dihydropyrimidine Dehydrogenase
Previous Article in Special Issue
Decisive Interactions between the Heterocyclic Moiety and the Cluster Observed in Polyoxometalate-Surfactant Hybrid Crystals
Article Menu
Issue 4 (April) cover image

Export Article

Open AccessArticle
Int. J. Mol. Sci. 2015, 16(4), 8896-8933; doi:10.3390/ijms16048896

Chemical Bonding: The Orthogonal Valence-Bond View

Department of Chemistry, University of Graz, Heinrichstrasse 28, 8010 Graz, Austria
Academic Editor: Charles L. Perrin
Received: 29 January 2015 / Revised: 17 March 2015 / Accepted: 31 March 2015 / Published: 21 April 2015
(This article belongs to the Special Issue Chemical Bond and Bonding 2015)

Abstract

Chemical bonding is the stabilization of a molecular system by charge- and spin-reorganization processes in chemical reactions. These processes are said to be local, because the number of atoms involved is very small. With multi-configurational self-consistent field (MCSCF) wave functions, these processes can be calculated, but the local information is hidden by the delocalized molecular orbitals (MO) used to construct the wave functions. The transformation of such wave functions into valence bond (VB) wave functions, which are based on localized orbitals, reveals the hidden information; this transformation is called a VB reading of MCSCF wave functions. The two-electron VB wave functions describing the Lewis electron pair that connects two atoms are frequently called covalent or neutral, suggesting that these wave functions describe an electronic situation where two electrons are never located at the same atom; such electronic situations and the wave functions describing them are called ionic. When the distance between two atoms decreases, however, every covalent VB wave function composed of non-orthogonal atomic orbitals changes its character from neutral to ionic. However, this change in the character of conventional VB wave functions is hidden by its mathematical form. Orthogonal VB wave functions composed of orthonormalized orbitals never change their character. When localized fragment orbitals are used instead of atomic orbitals, one can decide which local information is revealed and which remains hidden. In this paper, we analyze four chemical reactions by transforming the MCSCF wave functions into orthogonal VB wave functions; we show how the reactions are influenced by changing the atoms involved or by changing their local symmetry. Using orthogonal instead of non-orthogonal orbitals is not just a technical issue; it also changes the interpretation, revealing the properties of wave functions that remain otherwise undetected. View Full-Text
Keywords: bonding; bond; theoretical entity; VB; OVB; interference; VB reading; diabatic processes bonding; bond; theoretical entity; VB; OVB; interference; VB reading; diabatic processes
Figures

Figure 1

This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

Scifeed alert for new publications

Never miss any articles matching your research from any publisher
  • Get alerts for new papers matching your research
  • Find out the new papers from selected authors
  • Updated daily for 49'000+ journals and 6000+ publishers
  • Define your Scifeed now

SciFeed Share & Cite This Article

MDPI and ACS Style

Sax, A.F. Chemical Bonding: The Orthogonal Valence-Bond View. Int. J. Mol. Sci. 2015, 16, 8896-8933.

Show more citation formats Show less citations formats

Related Articles

Article Metrics

Article Access Statistics

1

Comments

[Return to top]
Int. J. Mol. Sci. EISSN 1422-0067 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top