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

: 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 ener...

• Type: Journal
• Year: 2007
• Where: JCC
• Authors: Jean-Paul Malrieu, Nathalie Guihéry, Carmen jiménez Calzado, Celestino Angeli
• Keywords: Dynamical Correlation Effect, JCC 2007, Valence Bond Decomposition, Valence Electronic Population