Relative contribution of combined kinetic and exchange energy terms vs the electronic component of molecular electrostatic potential in hardness potential derivatives

摘要

The relative contribution of the sum of kinetic [(10/9)CFρ(rì..)2/3] and exchange energy [(4/9)CXρ(rì..)1/3] terms to that of the electronic part of the molecular electrostatic potential [Vel(rì..)] 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.