Journal of Physical Chemistry A, Vol.110, No.25, 7913-7917, 2006
Modern valence-bond-like representations of selected D-6h "aromatic" rings
Starting from CASSCF( 6,6)/6-31G(d,p) wave functions, we consider different valence-bond (VB)-like interpretations of the d electron systems for various ( constrained) "benzene-like" D-6h rings, exploiting the invariance of the total wave function to arbitrary nonsingular transformations of the active orbitals. Quantities obtained rather directly from the various calculations provide a fairly consistent ordering of the degree of aromaticity: C6H6 similar to B-6 > N-6 > Al-6 similar to Si6H6 > P-6. Representations based on mutually orthogonal orbitals are found to be somewhat less satisfactory than those that have no such constraints on the overlaps between the active orbitals.