Energetics of Electron Pairs in Electrophilic Aromatic Substitutions

The interacting quantum atoms approach (IQA) as applied to the electron-pair exhaustive partition of real space induced by the electron localization function (ELF) is used to examine candidate energetic descriptors to rationalize substituent effects in simple electrophilic aromatic substitutions. It is first shown that inductive and mesomeric effects can be recognized from the decay mode of the aromatic valence bond basin populations with the distance to the substituent, and that the fluctuation of the population of adjacent bonds holds also regioselectivity information. With this, the kinetic energy of the electrons in these aromatic basins, as well as their mutual exchange-correlation energies are proposed as suitable energetic indices containing relevant information about substituent effects. We suggest that these descriptors could be used to build future reactive force fields.

Automated summary

The interacting quantum atoms approach is used to examine energetic descriptors for rationalizing substituent effects in electrophilic aromatic substitutions. The decay mode of aromatic valence bond basin populations and the fluctuation of adjacent bonds can provide information about inductive and mesomeric effects. The kinetic energy of electrons in aromatic basins, as well as their mutual exchange-correlation energies, are proposed as suitable energetic indices containing relevant substituent effects information.