Solvent effect on stabilization energy: An approach based on density functional reactivity theory

Abstract

In the present article a formalism and the corresponding computational method is developed to take care of the variation of stabilization energy with solvent polarity in the process of adduct formation. For this purpose, a simple but physically insightful definition of “net desolvation energy” is proposed keeping in mind the sequence of events taking place in the process of adduct formation in a solvent. The approach used here is based on density functional reactivity theory (DFRT) and the representative samples chosen are adduct formation between (a) methyltrioxorhenium (MTO) and pyridine and (b) (azidomethyl)benzene and methylpropiolate. The generated data in case (a) is correlated with already known experimental parameter that is, formation constant (Kf). The observed trends claim that with the increase in solvent polarity interaction (or stabilization) energy becomes less negative which means that on increasing the solvent polarity the chances of adduct formation are less. This is further supported by calculating hardness values of adducts in different solvents which goes on decreasing with the increase in solvent polarity. Here, the computed data show that on increasing the polarity (i.e., dielectric constant) of the solvent, the “net desolvation energy” increases. Finally, when “net desolvation energy” is added to the stabilization energy obtained from DFRT the predicted trends are achieved.

DFT Analysis of Charge Distribution and Electrostatic Potential in SiO 2 Ring Clusters with Different Planar Folds

“…The electrostatic potential energy maps of nanoscale SiO2 ring clusters can be used to predict their reactivity by using density functional theory (DFT) [10]. DFT analysis allows for the calculation of charge states, bond lengths, and total energies of clusters, providing valuable information about their electronic structure [11].…”

Preferential Solvation of 4-Carboxyl-2, 6-Dinitrophenylazohydroxynaphthalenes in Mixed Hydroxylic Solvents

“…Solvents influence reaction course and rates largely in two ways viz. their effects on equilibrium properties of the reaction including the stabilization/destabilization of the products, reactants, activated complexes or activation energy and secondly their non-equilibrium or dynamic effects on reactions (Ahmad et al, 2015;Hamid and Roy, 2019). Thus, the use of solvent mixtures to achieve desired solvent properties is common for practical purposes including separation/purification procedures in organic synthesis and to dictate the rates of formation (Sasirekha et al, 2008;Gupta et al, 2017).…”

Correlation between Equilibrium Constant and Stabilization Energy: A Combined Approach Based on Chemical Thermodynamics, Statistical Thermodynamics, and Density Functional Reactivity Theory

“…The numerical support in favor of the conjecture was provided after introducing a new parameter termed as "net desolvation energy", which happens to be the negative of "net free energy of solvation". 14 It is well-known that the extent of interaction between the electron acceptor (A) and the electron donor (B) is measured by equilibrium constant (K) of the equilibrium A + B ⇌ AB. So, in principle, the K values of the interaction (or reaction) between A and B in the process of adduct (or Lewis adduct) 15 formation can be correlated to the stabilization energy values generated by the CDASE scheme.…”

“…The extended formalism also conjectured the effect of solvent polarity on stabilization energy. The numerical support in favor of the conjecture was provided after introducing a new parameter termed as “net desolvation energy”, which happens to be the negative of “net free energy of solvation” …”