Orbital-Weighted Dual Descriptor for the Study of Local Reactivity of Systems with (Quasi-) Degenerate States

An alternative response function, based on the dual descriptor in terms of Koopmans approximation, is hereby proposed for the description of chemical reactivity in systems with (quasi-) degenerate frontier molecular orbitals. This descriptor is constructed from Fukui functions that include contributions from different orbitals, i.e., orbital-weighted Fukui functions. The methodology is applied to three case studies: the first case consists of a series of benchmark organic and inorganic molecules from which the dual descriptor, based only on frontier orbitals, is not appropriate to describe their reactivity. The second case deals with the proper description of chemical reactivity in Diels-Alder reactions between fullerene C60 and cyclopentadiene (CP), revealing the importance of considering secondary orbital interactions for an adequate regioselectivity description. The third, and last case, consists of a series of polycyclic aromatic hydrocarbons (PAHs) possessing molecular orbital degeneracy. By means of analyzing of this descriptor, an alternative approach to the description of aromaticity is proposed. In all cases, the proposed index called "orbital-weighted dual descriptor" has proven to accurately describe the chemical reactivity and aromaticity of the studied systems. © 2019 American Chemical Society.