Relative Contribution of Combined Kinetic and Exchange Energy Terms vs the Electronic Component of Molecular Electrostatic Potential in Hardness Potential Derivatives

Abstract

The relative contribution of the sum of kinetic [(10/9)CFρ(r̅)2/3] and exchange energy [(4/9)CXρ(r̅)1/3] terms to that of the electronic part of the molecular electrostatic potential [Vel(r̅)] in the variants of hardness potential is investigated to assess the proposed definition of Δ+h(k) = −[VelN+1(k) – VelN(k)] and Δ–h(k) = −[VelN(k) – VelN–1(k)] (Saha; et al. J. Comput. Chem. 2013, 34, 662). Some substituted benzenes and polycyclic aromatic hydrocarbons (PAHs) (undergoing electrophilic aromatic substitution), carboxylic acids, and their derivatives are chosen to carry out the theoretical investigation as stated above. Intra- and intermolecular reactivity trends generated by Δ+h(k) and Δ–h(k) are found to be satisfactory and are correlated reasonably well with experimental results.