Collect. Czech. Chem. Commun. 2008, 73, 481-506

Handling Electrostatic Interactions in Molecular Simulations: A Systematic Study

Jiří Kolafaa, Filip Moučkab and Ivo Nezbedab,c,*

a Department of Physical Chemistry, Institute of Chemical Technology, Prague, 166 28 Prague 6, Czech Republic
b Faculty of Science, J. E. Purkinje University, 400 96 Ústí nad Labem, Czech Republic
c E. Hála Laboratory of Thermodynamics, Institute of Chemical Process Fundamentals, Academy of Sciences of the Czech Republic, 165 02 Prague 6, Czech Republic


Two qualitatively different models with strong long-range electrostatic interactions, Lennard-Jones diatomics with an embedded dipole moment and TIP4P/2005 water, are considered in extensive Monte Carlo and molecular dynamics simulations to systematically study the differences in results caused by different treatments of the long-range electrostatic interactions. In addition to the standard Ewald summation and reaction field methods, we consider also two variants of short-range approximations. Both thermodynamic and structural properties, and both homogeneous and inhomogeneous phases are considered. It is shown that the accuracy of the short-range approximations with carefully selected parameters may be sufficient for a number of applications; however, in some cases one can encounter accuracy limits or structural or other artifacts.

Keywords: Molecular simulation; Ewald summation; Reaction field; Long-range interactions; Electrostatic forces.

References: 33 live references.