Efficiency of electrostatic and steric forces in theoretical appreciating chemical reactivity-related phenomena

Abstract

ABSTRACTRationalisation of computational results towards appreciating and predicting chemical reactivity is a topic worthy of investigation in theoretical chemistry. In this regard, a robust and generally applicable framework to comprehend the problem is still lacking. Nevertheless, on the basis of a density functional theory (DFT) energy partition scheme where the total electronic energy is decomposed into three independent effects as steric, electrostatic and the fermionic quantum, the fundamental driving forces of chemical processes to understand molecular reactivity have recently been proposed. In the present contribution, the two related descriptors, electrostatic and steric forces, are utilised to evaluate their applicability and accountability to comprehend different chemical reactivity properties. To do so, we have considered the electrophilic and nucleophilic regioselectivity, stereoselectivity and etherification reaction of phenolic derivatives as illustrative examples of reactivity-related phenomena. Highlighting the distinguished characteristics of the descriptors under study, their usefulness for analysing the chemical reactivity properties and reproducing experimental evidences is showcased. On the whole, our findings corroborate that the DFT energy partitioning scheme and the associated reactivity descriptors can pave the way towards theoretical rationalisation of chemical reactivity-related phenomena.