On the three-center orbital projection formalism within the electron density of delocalized bonds method

A new development of the Electron Density of Delocalized Bonds formalism (EDDB) is proposed that provides marked improvement in the description of electron delocalization in aromatic rings. Special attention is paid to charged aromatic hydrocarbons of different size, for which the total population of electrons delocalized between adjacent bonds from the original formulation of the EDDB method significantly overestimates the multicenter it-electron sharing effects. The revised bond-orbital projecting scheme gives rise to systematic improvement of the results of the EDDB analysis, which now supports findings by other researchers. (C) 2016 Elsevier B.V. All rights reserved.