New values for the absolute solvation free energy of univalent ions in aqueous solution

Solvation of monovalent anions in acetonitrile and N,N-dimethylformamide: Parameterization of the IEF-PCM model

“…Solvation of the F À anion in AN produced a value for the solvation free energy that is 1.2 kcal/mol higher than the experimental value. If we take into account that the uncertainty associated with the experimental value in the solvation energy for this anion is approximately ±1.6 kcal/mol [31,59], we consider our theoretical result in excellent agreement with experiment. In DMF, we obtained a value exhibiting a positive deviation of 7.7 kcal/mol.…”

A Theoretical Analysis of the Free-Energy Profile of the Different Pathways in the Alkaline Hydrolysis of Methyl Formate In Aqueous Solution

“…Finally, experimental values for solvation free energies were taken from our recent paper. [27] These data were combined to determine the gas-phase and aqueous solution reaction free energies for the hydrolysis and the decarbonylation reactions, and are indicated in Table 5.…”

“…[3,11,26] The common approach, in which a molecule is represented by its gas-phase structure, and the free energy of solvation is calculated from a reaction field model is usually inadequate for ions in aqueous media and can lead to inaccurate results for the free energy of solvation of ions. [27] This is due to the shortcomings of continuum models [36] in properly accounting for strong electrostatic interactions and hydrogen bonding with some of the nearby neutral solvent molecules. This situation can be overcome in principle by addition of some explicit solvent molecules around the bare ion to form a cluster, or supermolecule, where specific solute ± solvent interactions can be introduced in the theoretical model.…”

“…Our analysis is based on a clustercontinuum method to calculate the free energy of solvation of ions, a hybrid approach recently proposed by us and tested for several organic ions. [27,28] We have shown this approach to be more stable than pure continuum models, and to yield good results for ionic species. In the first part of this paper, the details of the calculations are outlined, whereas in the second section we show how to apply the cluster-continuum model to chemical reactions.…”

Density functional theoretical study of pKa of RCOOH (RH, CH3, and C2H5) using the combination of the extended clusters‐continuum model

“…The usual approach is to make use of the experimental absolute solvation free energy of the proton [8,9]. To overcome this problem, relative pK a calculations can be done according to the following process.…”