Comparison of the AIM Delocalization Index and the Mayer and Fuzzy Atom Bond Orders

Abstract

In this paper the behavior of three well-known electron-sharing indexes, namely, the AIM delocalization index and the Mayer and fuzzy atom bond orders are studied at the Hartree-Fock level. A large number of five-membered ring molecules, containing several types of bonding, constitute the training set chosen for such purpose. A detailed analysis of the results obtained shows that the three indexes studied exhibit strong correlations, especially for homonuclear bonds. The correlation is somewhat poorer but still significant for polar bonds. In this case, the bond orders obtained with the Mayer and fuzzy atom approaches are normally closer to the formally predicted bond orders than those given by the AIM delocalization indexes, which are usually smaller than those expected from chemical intuition. In some particular cases, the use of diffuse functions in the calculation of Mayer bond orders leads to unrealistic results. In particular, noticeable trends are found for C-C bonds, encouraging the substitution of the delocalization index by the cheaper fuzzy atom or even the Mayer bond orders in the calculation of aromaticity indexes based on the delocalization index such as the para-delocalization index and the aromatic fluctuation index.