Critical study of the charge transfer parameter for the calculation of interaction energy using the local hard-soft acid-base principle.

Local hard–soft acid–base (HSAB) principle is semiquantitative in nature due to the presence of an ad hoc charge transfer parameter. The accuracy of HSAB principle significantly depends on the definition of this ad hoc parameter. In this paper, for the first time we have introduced the second-order approximation of ΔN (ΔNsecond) as an ad hoc parameter for charge transfer to calculate interaction energies of multiple site based interactions using local hard soft acid base principle. The second-order approximation of ΔN has been derived from Sanderson’s electronegativity equalization principle. To validate our approach, we have studied interaction energies of some prototype molecules. The interaction energies obtained from our approach have been further compared with the interaction energies of those obtained using other charge transfer parameters (ΔNfirst and λ) and the conventional methods. We have also discussed the advantages and limitations of the approach.