On the interpretation of valence bond wavefunctions.
Valence bond wavefunctions are naturally geared to the chemist's idea of chemical bonding. In a structure one may distinguish different electron pair bonds and possible radical character. A structure may correspond to a covalent bond, where all electrons are equally divided over the atoms, or may describe an excess charge on a discrete part of the molecule, which indicates ionic bond character. From the weights of the structure in a variationally optimised multi-structure valence bond wavefunction one may derive the importance of the different bonding types. The individual structures could be considered to represent the different physical situations. We explore this concept for simple diatomic molecules and for polyatomics, and we discuss the relation to Lewis structures. We show that the assumption of individual properties for the individual structures leads to inconsistencies.
Havenith
Remco W A
RW
Theoretical Chemistry Group (Affiliated to Organic Chemistry and Catalysis), Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands. r.w.a.havenith@chem.uu.nl
van Lenthe
Joop H
JH
Jenneskens
Leonardus W
LW
Engelberts
Jeroen J
JJ