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(r)2/3] and exchange energy [(4/9)CXρ(r)1/3] terms to that of the electronic part of the molecular electrostatic potential [Vel(r)] 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.

On the trends of Fukui potential and hardness potential derivatives in isolated atoms vs. atoms in molecules

“…(6) and 7) and Fukui potential (Eqns. 3and 4 of reasonably high reactivity (as already determined experimentally [42][43][44][45][46][47][48][49][50][51][52] and some of them are verified by theoretical methods also 30,32,43,49 ). Numbering of atoms in most of the systems chosen is as per standard numbering convention.…”

“…31 The mathematical definition of ) r ( h requires some detailed approximations which is discussed elsewhere. 30,32 The approximated analytical form of hardness potential [ ] to explain both intermolecular and intramolecular reactivity trends of systems having variation of atom types of the reactive centres, different sizes (i.e., number of electrons) and characteristics. 30 The main advantage of taking the left and right derivative of ) r ( h is to make a difference between the processes of gaining or loosing electron density and when this is applied to Eq.…”

“…31 The mathematical definition of h(% r) requires some detailed approximations which is discussed elsewhere. 30,32 The approximated analytical form of hardness potential [h(% r)] is,…”

Negativity of Fukui function of some isolated s and p block elements: The role of orbital relaxation effect

“…A c c e p t e d M a n u s c r i p t 6 valued in regions where the highest occupied molecular orbital (HOMO) (for ) or the lowest unoccupied molecular orbital (LUMO) ) (for ) have nodal surfaces and some atomic and molecular examples are discussed in literature [9,13,[25][26][27][28][29][30][31][32][33]. Usually, the most negative values are located at the site where electron-nuclear attraction potential is highest [9].…”

Contribution to Reactivity, Stability and Selectivity of Monodentated Free Phosphines

“…Its efficiency and accuracy in the evaluation of a number of molecular properties [10] have been recognized by all. Moreover, the examination and proper exploitation of frontier orbital energies (SOMO) guided the understanding of the chemical reactivity of free and complexed phosphines by Lee et al by manipulating the electronic density as a fundamental quantity [11][12][13]. This work is part of the design and synthesis of new series of phosphine-based organic semiconductors.…”