Accurate experimental values for the free energies of hydration, or the free energies of solvation, of the H+, OH-, and H3O ions are of fundamental importance. By use of the most accurate value for the free energy of solvation of H+, the known value for the free energy of solvation of water, and the known values for the gas phase and aqueous phase deprotonation of water, the corresponding exper...

This work introduces a model, solvation model 6 with temperature dependence (SM6T), to predict the temperature dependence of aqueous free energies of solvation for compounds containing H, C, and O in the range 273-373 K. In particular, we extend solvation model 6 (SM6), which was previously developed (Kelly, C. P.; Cramer, C. J.; Truhlar, D. G. J. Chem. Theory Comput. 2005, 1, 1133) for predict...

Molecular dynamicdfree energy perturbation simulations of several small amides [acetamide (ACT), N-methylacetamide (NMA), and N,N-dimethylacetamide] and amines [NH3, NH2CH3, NH(CH3)2, and N(CH3)3] in aqueous solution were performed to study the effects on solvation free energies arising from N-methylation. Using pairwise additive potentials, a uniform pattern of solvation effects was always obt...

The solvation energy and entropy at infinite dilution consist of a solute-solvent term and a solvent reorganization term representing the contributions of changes in solvent structure upon solute insertion. In the standard, homogeneous treatment of solutions, changes in solvent structure are expressed through derivatives of the homogeneous pair correlation function, which are very difficult to ...

An algorithm is developed for performing calculations for the nonlocal electrostatic solvation theory of an ion in a cavity, accounting for electrostatic boundary conditions. The latter implies an induced charge distribution on the cavity surface as well as an induced volume charge distribution in the medium. This approach is validated by a variational derivation which also provides a general e...

A nonlocal continuum theory of solvation is applied using an oscillating dielectric function with spatial dispersion. It is found that a convergent solution cannot be calculated using a model of a fixed solute cavity inside the solvent continuum. This is attributed to the fact that the dielectric oscillations appear as a result of coupling between polarization and density fluctuations, contradi...

We analyze de ciencies of commonly used Coulomb approximations in Generalized Born solvation energy calculation models and report a development of a new fast surface-based method (FSBE) for numerical calculations of the solvation energy of biomolecules with charged groups. The procedure is only a few percents wrong for molecular con gurations of arbitrary sizes, provides explicit values for the...

Thermochemical cycles that involve pKa, gas-phase acidities, aqueous solvation free energies of neutral species, and gas-phase clustering free energies have been used with the cluster pair approximation to determine the absolute aqueous solvation free energy of the proton. The best value obtained in this work is in good agreement with the value reported by Tissandier et al. (Tissandier, M. D.; ...

We develop a linear response theory of solvation of ionic and dipolar solutes in anisotropic, axially symmetric polar solvents. The theory is applied to solvation in polar nematic liquid crystals. The formal theory constructs the solvation response function from projections of the solvent dipolar susceptibility on rotational invariants. These projections are obtained from Monte Carlo simulation...