Directionality and additivity effects of molecular acidity and aromaticity for substituted benzoic acids under external electric fields

Our recent study [M. Li et al.Phys. Chem. Chem. Phys., 2023, 25, 2595-2605] unveiled that the impact of an external electric field on molecular acidity and aromaticity for benzoic acid is directional, which can be understood using changes in frontier orbitals and partial charges. However, it is unclear if the effect will disappear when substituting groups are present and whether new patterns of changes will show up. In this work, as a continuation of our efforts to appreciate the impact of external electric fields on physiochemical properties, we find that the directionality effect is still in place for substituted benzoic acid derivatives and that there exists the additivity effect with respect to the number of substituent groups, regardless of the direction of the applied field and the type of substituting groups. We confirm the findings using electron-donating and electron-accepting groups with the electric field applied either parallelly or perpendicularly to the carboxyl group along the benzene ring. The directionality and additivity effects uncovered from this work should enrich the body of our knowledge about the impact of external electric fields on physiochemical properties and could be applicable to other systems and properties as well. Direction and sum rules are key features of acidity and aromaticity for substituted benzoic acids in external electric fields.

Automated summary

This study reveals that the impact of an external electric field on the acidity and aromaticity of benzoic acid has directionality and additivity effects. These findings enrich our knowledge of the influence of external electric fields on physiochemical properties and have potential applications in other systems and properties.