Bond electron pair: Its relevance and analysis from the quantum chemistry point of view

✍ Scribed by Jean-Paul Malrieu; Nathalie Guihéry; Carmen jiménez Calzado; Celestino Angeli

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 450 KB
• Volume: 28
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20546

✦ Synopsis

Abstract

This paper first comments on the surprisingly poor status that Quantum Chemistry has offered to the fantastic intuition of Lewis concerning the distribution of the electrons in the molecule. Then, it advocates in favor of a hierarchical description of the molecular wave‐function, distinguishing the physics taking place in the valence space (in the bond and between the bonds), and the dynamical correlation effects. It is argued that the clearest pictures of the valence electronic population combine two localized views, namely the bond (and lone pair) Molecular Orbitals and the Valence Bond decomposition of the wave‐function, preferably in the orthogonal version directly accessible from the complete active space self consistent field method. Such a reading of the wave function enables one to understand the work of the nondynamical correlation as an enhancement of the weight of the low‐energy VB components, i.e. as a better compromise between the electronic delocalization and the energetic preferences of the atoms. It is suggested that regarding the bond building, the leading dynamical correlation effect may be the dynamical polarization phenomenon. It is shown that most correlation effects do not destroy the bond electron pairs and remain compatible with Lewis' vision. A certain number of free epistemological considerations have been introduced in the development of the argument. © 2006 Wiley Periodicals, Inc. J Comput Chem 2007