Extension of MST/SCRF method to organic solvents:Ab initio and semiempirical parametrization for neutral solutes in CCl4

Abstract

The self‐consistent reaction field (SCRF) method proposed by Miertus, Scrocco, and Tomasi (MST) was extended to solutions of neutral solutes in CCl4. A detailed parametrization of the solute/solvent interface and of the “hardness” atomic parameters determining the van der Waals interactions was performed from comparison with experimental data and Monte Carlo simulations. The parametrization was carried out at both ab initio (6‐31G*) and semiempirical (MNDO, AM1, PM3) levels. The MST/SCRF optimized versions provide accurate estimates of the free energy of solvation in CCl4 for the series of molecules studied. Furthermore, a precise description of the solvent effect on different chemical processes in CCl4 solution supports the reliability of the parametrization. © 1996 by John Wiley & Sons, Inc.

Performance of the IEF-MST solvation continuum model in the SAMPL2 blind test prediction of hydration and tautomerization free energies

“…Finally, DG vW is computed using a linear relationship to the solvent-exposed surface of each atom (Eq. 5) [20][21][22][23][24], where the atomic surface tensions are determined by fitting to a set of experimental free energies of solvation…”

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

“…The gas phase optimized geometries were used in the liquid phase calculations without any corrections. It has been noted that the use of gas phase geometries in the calculations for the solvation process does not introduce significant errors when compared to geometries optimized in solution [25].…”

“…Generally, this scaling factor is chosen by maximizing the agreement between experimental data and computed values of some property for a representative group of solutes in a given solvent. Several parameterizations of the PCM, which make directly use of atomic radii and a suitable scaling factor, are described in the literature for the solvation processes of neutral molecules in water [16] and organic solvents such as chloroform [24], carbon tetrachloride [25], and octanol [26].…”

Theoretical and experimental 13C and 15N NMR investigation of guanylhydrazones in solution

“…34,35 The problem is shifted to the size of the spheres, and several studies have shown that standard van der Waals radii provide reasonable cavity sizes. 36 This situation results in difficulties for the continuum model to represent some apolar solvents, e.g. cyclohexane.…”