Electrostatic Potentials and Free Energies of Solvation of Polar and Charged Molecules

  title={Electrostatic Potentials and Free Energies of Solvation of Polar and Charged Molecules},
  author={Gerhard Hummer and Lawrence R Pratt and Angel Enrique Garcia and Bruce J. Berne and Steven W. Rick},
  journal={Journal of Physical Chemistry B},
Theories of solvation free energies often involve electrostatic potentials at the position of a solute charge. Simulation calculations that apply cutoffs and periodic boundary conditions based on molecular centers result in center-dependent contributions to electrostatic energies due to a systematic sorting of charges in radial shells. This sorting of charges induces a surface-charge density at the cutoff sphere or simulation-box boundary that depends on the choice of molecular centers. We… 
Calculation of ionic charging free energies in simulation systems with atomic charges, dipoles, and quadrupoles
The ionic charging free energy is a very sensitive probe for the treatment of electrostatics in any given simulation setting. In this work, we present methods to compute the ionic charging free
Polarization around an ion in a dielectric continuum with truncated electrostatic interactions
In order to reduce computational effort and to allow for the use of periodic boundary conditions, electrostatic interactions in explicit solvent simulations of molecular systems do not obey Coulomb’s
Ionic charging free energies: Spherical versus periodic boundary conditions
Ionic charging free energies calculated by Ewald summation differ substantially from those calculated in spherical cluster calculations, with or without the inclusion of a Born correction in the
The Role of Broken Symmetry in Solvation of a Spherical Cavity in Classical and Quantum Water Models.
The physical interpretation of the electrostatic potential difference between the region near the cavity and the bulk and its calculation are clarified and will have direct consequences toward the understanding of the thermodynamics of ion solvation through the cavity charging process.
The Influence of Distant Boundaries on the Solvation of Charged Particles
The long-ranged nature of the Coulomb potential requires a proper accounting for the influence of even distant electrostatic boundaries in the determination of the solvation free energy of a charged
Computation of methodology-independent ionic solvation free energies from molecular simulations. I. The electrostatic potential in molecular liquids.
The goal of the present article is to settle this long-standing controversy by carefully analyzing (both analytically and numerically) the properties of the electrostatic potential in molecular liquids (and inside cavities within them).
An Overview of Electrostatic Free Energy Computations for Solutions and Proteins.
Free energy simulations for electrostatic and charging processes in complex molecular systems encounter specific difficulties owing to the long-range, 1/r Coulomb interaction, but these issues can be handled with established computational protocols and illustrated for several small ions and three solvated proteins.
Computation of methodology-independent ionic solvation free energies from molecular simulations. II. The hydration free energy of the sodium cation.
The present article has shown that correction terms can be derived for the effect of an incorrect solvent polarization around the ion due to the use of an approximate (not strictly Coulombic) electrostatic scheme.
Incorporating the excluded solvent volume and surface charges for computing solvation free energy
To mimic the near‐solute dielectric polarization from MD simulations, the first‐shell water was treated as two layers of surface charges, the densities of which are proportional to the electric field at the solvent molecule that is modeled as a hard sphere.
Application of the Linearized MD Approach for Computing Equilibrium Solvation Free Energies of Charged and Dipolar Solutes in Polar Solvents
The linearized MD technique is developed in order to treat systematically free energies of simple charged and dipolar solutes in water. The solvent electrostatic response field in the solute region


Thermodynamics. An Advanced Treatment for Chemists and Physicists
Preface. Important symbols. General physical constants. Defined values and conversion factors. Introduction concerning notation and terminology. 1. Fundamental principles. 2. Digression on