Solv: An Alternative Continuum Model Implementation Based on Fixed Atomic Charges, Scaled Particle Theory, and the Atom–Atom Potential Method

Abstract

An alternative continuum model implementation is reported. The electrostatic contribution to the solvation Gibbs free energy utilizes the noniterative conductor-like screening model of Vyboishchikov and Voityuk

From a humorous post to a detailed quantum-chemical study: isocyanate synthesis revisited

“…6. The polarity of the solvent increases with increasing e and E T (30), and as we can see from the results, the increase of the polarity of the solvent decreases the effective reaction barrier, making the reaction faster. It is worth noting that the effect of solvent polarity on the effective reaction barrier height is not dramatic since the maximum difference observed for water (the most polar solvent studied) is still less than 1 kcal mol À1 .…”

“…4 and 5). For this, we took the gas-phase calculation of the reaction at the DLPNO-CCSD(T)/CBS// r 2 SCAN-3c level of theory and used the recently developed Solv model, 30 applied in the SPT-V scheme. We have selected 28 of the most common laboratory solvents, ranging from nonpolar (hexane, carbon disulfide) to the most polar (water).…”

“…68,69 Along with DFT, optimizations of the structures and search for TS were done with the MP2 method. 70 Solvation effects were accounted for using the conductor-like polarizable continuum model (CPCM), 71,72 Conductor-like Screening Model (COSMO), [73][74][75] and a recently developed Solv model, 30 applied in the SPT-V scheme. Based on the DFT geometries, the accurate singlepoint energies of the structures were obtained using the DLPNO-CCSD(T) level of theory, 76 including the CPCM-based results.…”

“…[31][32][33][34][35] The full list of the studied solvents, as well as the corresponding dielectric constant and Reichardt's parameter values, can be found in the ESI. † The correlations of the effective barrier heights (eqn (2)) with solvents' dielectric constants e and Reichardt's E T (30) parameters are shown in Fig. 6.…”

“…6 Survey of changes in the effective reaction free energy barrier (eqn (2)) for 42 solvents of various polarities. The gas-phase energies were computed at the DLPNO-CCSD(T)/CBS//r 2 SCAN-3c level, while the free-energy correction for solvation was computed within the Solv model 30 applied in the SPT-V scheme. Sulfolane has been excluded from the correlation plot with E T (30) parameters since, to the best of our knowledge, no value for it has been reported in the literature so far.…”