Continuum solvent calculations of pKas and reduction potentials usually entail the use of a thermodynamic cycle to express the reaction free energy in terms of gas phase energies and free energies of solvation. In this work, we present a systematic study comparing the solution phase free energy changes obtained in this manner with those directly computed within the SMD solvation model against a...

The solvation characteristic of 2-methoxy-4-aminobenzoic acid methyl ester (MABAE) and 2methoxy-4-dimethylaminobenzoic acid methyl ester (MDABAE) in the S0, S1(LE) and S1(ICT) states has been determined by means of solvatochromic shifts in neat and binary solvent mixtures. The multiple linear regression analysis of Kamlet et al. indicates that non-specific dielectric dipoledipole and specific h...

Central in a variational implicit-solvent description of biomolecular solvation is an effective free-energy functional of the solute atomic positions and the solute-solvent interface (i.e., the dielectric boundary). The free-energy functional couples together the solute molecular mechanical interaction energy, the solute-solvent interfacial energy, the solute-solvent van der Waals interaction e...

Statistical thermodynamics provides a powerful theoretical framework for analyzing, understanding and predicting the conformational properties of biomolecules. The central quantity is the potential of mean force or effective energy as a function of conformation, which consists of the intramolecular energy and the solvation free energy. The intramolecular energy can be reasonably described by mo...

A novel method for fast and accurate evaluation of the generalized Born radii in macromolecular solvation electrostatics calculations is proposed, based on the solvent accessibility of the first two solvation layers around an atom. The reverse generalized Born radii calculated by the method have correlation coefficient of 98.7% and RMSD of 0.031 A(-1) with the values obtained using a precise bu...

The stepwise solvation-equilibrium model of Stokes and Robinson isused for a description of departures from ideality in ionic solutions. It is shown howto construct a thermodynamically consistent model including solvation effects. Sim-ple expressions are derived for the mean ion solvation number. The model is appliedto strong electrolyte solutions (pure water+salt and mixed aque...

In an implicit-solvent description of the solvation of charged molecules (solutes), the electrostatic free energy is a functional of concentrations of ions in the solvent. The charge density is determined by such concentrations together with the point charges of the solute atoms, and the electrostatic potential is determined by the Poisson equation with a variable dielectric coefficient. Such a...