A Real‐Space Force Analysis of Chemical Bonding and SN2 Reactivity From Exchange‐Correlation Potentials

ABSTRACT

The nature of chemical bonding and chemical reactivity can be described from the spatial organization of electronic forces acting in real space. Here, the force‐field framework based on one‐electron potentials is extended to molecular bonding and to the evolution of an SN2 reaction. Exchange, correlation, electrostatic, and PAEM potentials, together with their associated force fields, were analyzed for reference diatomic systems, a H _n Y–F series (Y = Li, Be, B, C, N, O; n  = 0–3) spanning different bonding regimes, and the F ⁻  + CH ₃ Cl → FCH ₃  + Cl ⁻ reaction along the intrinsic reaction coordinate. The results show that exchange dominates large regions of interatomic space, whereas correlation is especially sensitive to electronic reorganization in bonding regions. The corresponding force fields reveal the ionic‐to‐covalent transition and the concerted reorganization around forming FC and breaking CCl bonds, providing a physically grounded real‐space route to interpret bonding and reactivity.