Generation of Kekulé valence structures and the corresponding valence bond wave function

• Published in: Journal of computational chemistry 2011-03, Vol.32 (4), p.696-708
• Main Authors: Rashid, Zahid, van Lenthe, Joop H
• Format: Article
• Language: English
• Subjects: (poly)cyclic conjugated systems; Algorithms; Atoms & subatomic particles; Chemical bonds; computer algorithm; Fullerenes; generation of Kekulé valence structures; Kekulé valence structures; valence Bond Method
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.21655

A new scheme, called “list of nonredundant bonds”, is presented to record the number of bonds and their positions for the atoms involved in Kekulé valence structures of (poly)cyclic conjugated systems. Based on this scheme, a recursive algorithm for generating Kekulé valence structures has been developed and implemented. The method is general and applicable for all kinds of (poly)cyclic conjugated systems including fullerenes. The application of the algorithm in generating Valence Bond (VB) wave functions, in terms of Kekulé valence structures, is discussed and illustrated in actual VB calculations. Two types of VBSCF calculations, one involving Kekulé valence structures only and the second one involving all covalent VB structures, were performed for benzene, pentalene, benzocyclobutadiene, and naphthalene. Both strictly local and delocalised p-orbitals were used in these calculations. Our results show that, when the orbitals are restricted to their own atoms, other VB structures (Dewar structures) also have a significant contribution in the VB wave function. When removing this restriction, the other VB structures (Dewar and also the ionic structures) are accommodated in the Kekulé valence structures, automatically. Therefore, at VBSCF delocal level, the ground states of these systems can be described almost quantitatively by considering Kekulé valence structures only at a considerable saving of time.