Properties of aromaticity indices based on the one-electron density matrix.
Proper normalization of two previously published indices yields aromaticity measures that, when computed within the Hückel molecular orbital (HMO) approximation, closely match the topological resonance energies per pi electron of aromatic annulenes and their ions. The normalized indices, which quantify aromaticity of individual rings in polycyclic systems, are equally applicable to homocyclic and heterocyclic compounds and can be readily computed from 1-matrices calculated at any level of electronic structure theory. However, only the index ING, derived from the Giambiagi formula, produces proper ordering of aromaticities of heterocyclic compounds, provided it is calculated from all-electron wavefunctions in conjunction with the atoms in molecule (AIM) partitioning. Its values are shown to be strongly affected by electron correlation effects. Because of its apparent inability to distinguish between anti- and nonaromatic systems, ING should only be employed for aromatic species.
Cioslowski
Jerzy
J
Institute of Physics, University of Szczecin, Wielkopolska 15, 70-451 Szczecin, Poland. jerzy@kyoko.chem.fsu.edu
Matito
Eduard
E
Solà
Miquel
M