Can van der Waals constants be used in the chemical reactivity analysis? A new approach as a support to minimum magnetizability principle

Abstract

One of the most important purposes of theoretical chemists is to derive new, useful, and reliable equations to compute the well‐known parameters like hardness, polarizability, magnetizability, and electrophilicity providing enough hints for the reactivity analysis of the chemical systems. In the derivation of such equations, our research team widely considers the popular electronic structure rules like electronegativity equalization, maximum hardness, minimum polarizability, minimum magnetizability, and minimum electrophilicity principles. Recently, in the light of maximum entropy and minimum magnetizability principles, Kaya and Chattaraj (2021) presented a simple way to calculate their standard absolute entropies (S0298) based on molar diamagnetic susceptibilities (χm) of inorganic ionic systems. In the present paper, a new and useful molar diamagnetic susceptibility calculation method including the use of van der Waals constants (a and b) is introduced. Here, we named this method as Kaya–Şimşek approach. Through the relations between molar diamagnetic susceptibility and van der Waals constants, we can easily predict the magnetic susceptibility of molecules that their magnetic susceptibilities are unknown. The results of the equations derived are quite close to experimentally reported data. The analyses made proved that van der Waals constants can be considered as chemical reactivity descriptors. We propose that in stable states, van der Waals constants are minimized. The validity of minimum magnetizability principle is supported with solid evidences.

Density functional theory for exploration of chemical reactivity: Successes and limitations

“…Chakraborty et al 13 presented direct dynamics for the purpose of providing atomistic insights into the process of the collisional dynamics of O(3P) and dimethylamine (DMA) across the triplet electronic interface. Kaya et al 14 predicted the magnetic susceptibilities of substances on the basis of correlation among molar diamagnetic susceptibility and van der Waals constant. Liu et al 15 studied nine dimeric systems with various alkyl group sizes by using DFT approach.…”