Solvation/solvents free energy

Mean Unsigned Errors in Absolute Aqueous Solvation Gibbs Free Energies of Ions and Ion-Water Clusters, with a Single Water Molecule, for Various Continuum Solvent Models... 

In order to obtain a reliable value of the solute-solvent free energy, one has to compute this quantity by using the best possible shape of cavity which differs considerably from the ellipsoid. Therefore, after having computed the wavefunction with the ellipsoidal cavity, the solvation free energy is computed numerically by means of a realistic cavity, which is limited, in this instance, by an isodensity surface. Furthermore, in order to avoid the uncertainties on the energies of the isolated molecules, the solvation free energies are used to predict the modification of the equilibrium constant between the gas phase and the liquid phase. 

Similarly, changes must take place in the outer solvation shell diirmg electron transfer, all of which implies that the solvation shells themselves inliibit electron transfer. This inliibition by the surrounding solvent molecules in the iimer and outer solvation shells can be characterized by an activation free energy AG. ... 

For analysing equilibrium solvent effects on reaction rates it is connnon to use the thennodynamic fomuilation of TST and to relate observed solvent-mduced changes in the rate coefficient to variations in Gibbs free-energy differences between solvated reactant and transition states with respect to some reference state. Starting from the simple one-dimensional expression for the TST rate coefficient of a unimolecular reaction a— r... 

Within the framework of the same dielectric continuum model for the solvent, the Gibbs free energy of solvation of an ion of radius and charge may be estimated by calculating the electrostatic work done when hypothetically charging a sphere at constant radius from q = 0 q = This yields the Bom equation [13]... 

As with SCRF-PCM only macroscopic electrostatic contribntions to the Gibbs free energy of solvation are taken into account, short-range effects which are limited predominantly to the first solvation shell have to be considered by adding additional tenns. These correct for the neglect of effects caused by solnte-solvent electron correlation inclnding dispersion forces, hydrophobic interactions, dielectric saturation in the case of... 

Figure A3.8.3 Quantum activation free energy curves calculated for the model A-H-A proton transfer reaction described 45. The frill line is for the classical limit of the proton transfer solute in isolation, while the other curves are for different fully quantized cases. The rigid curves were calculated by keeping the A-A distance fixed. An important feature here is the direct effect of the solvent activation process on both the solvated rigid and flexible solute curves. Another feature is the effect of a fluctuating A-A distance which both lowers the activation free energy and reduces the influence of the solvent. The latter feature enliances the rate by a factor of 20 over the rigid case.

It is often the case that the solvent acts as a bulk medium, which affects the solute mainly by its dielectric properties. Therefore, as in the case of electrostatic shielding presented above, explicitly defined solvent molecules do not have to be present. In fact, the bulk can be considered as perturbing the molecule in the gas phase , leading to so-called continuum solvent models [14, 15]. To represent the electrostatic contribution to the free energy of solvation, the generalized Bom (GB) method is widely used. Wilhin the GB equation, AG equals the difference between and the vacuum Coulomb energy (Eq. (38)) ... 

The solvation free energy (AGgoi) is the free energy change to transfer a molecule fro vacuum to solvent. The solvation free energy can be considered to have three componen... 

The final class of methods that we shall consider for calculating the electrostatic compone of the solvation free energy are based upon the Poisson or the Poisson-Boltzmann equatior Ihese methods have been particularly useful for investigating the electrostatic properties biological macromolecules such as proteins and DNA. The solute is treated as a body of co stant low dielectric (usually between 2 and 4), and the solvent is modelled as a continuum high dielectric. The Poisson equation relates the variation in the potential (f> within a mediu of uniform dielectric constant e to the charge density p ... 

The constants K depend upon the volume of the solvent molecule (assumed to be spherica in slrape) and the number density of the solvent. ai2 is the average of the diameters of solvent molecule and a spherical solute molecule. This equation may be applied to solute of a more general shape by calculating the contribution of each atom and then scaling thi by the fraction of fhat atom s surface that is actually exposed to the solvent. The dispersioi contribution to the solvation free energy can be modelled as a continuous distributioi function that is integrated over the cavity surface [Floris and Tomasi 1989]. 

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