Topological Resonance Energies of Conjugated Structures

Abstract

AbstractThe graph‐theoretical backbone of the topological resonance energy (TRE) concept is outlined and the connection with the Dewar resonance energy (DRE) approach is described. It appears that the TRE is not a new aromaticity index, but an optimal DRE‐like quantity of great practical value for understanding and predicting the aromatic stability of conjugated structures. In the TRE concept the most important result is the introduction of the acyclic polynomial which closely approximates the acyclic‐polyene reference structure. The rules for the construction of the acyclic (reference) polynomial are presented. Application of TRE to monocyclic systems, to polycyclic molecules and their radicals and ions, to homoaromatic systems, and to excited states is discussed. In most cases the agreement between the theory and experimental findings is good. However, in some examples the predictions appear to be inconsistent with reported data. The reasons for the occasional anomalies in the TRE are investigated. In addition, the problem of normalization of the TRE is considered.