Dielectric response with short-ranged electrostatics

The dielectric nature of polar liquids underpins much of their ability to act as useful solvents, but its description is complicated by the long-ranged nature of dipolar interactions. This is particularly pronounced under the periodic boundary conditions commonly used in molecular simulations. In this article, the dielectric properties of a water model whose intermolecular electrostatic interactions are entirely short-ranged are investigated. This is done within the framework of local molecular-field theory (LMFT), which provides a well-controlled mean-field treatment of long-ranged electrostatics. This short-ranged model gives a remarkably good performance on a number of counts, and its apparent shortcomings are readily accounted for. These results not only lend support to LMFT as an approach for understanding solvation behavior, but also are relevant to those developing interaction potentials based on local descriptions of liquid structure.

Short solvent model for ion correlations and hydrophobic association

Coulomb interactions play a major role in determining the thermodynamics, structure, and dynamics of condensed-phase systems, but often present significant challenges. Computer simulations usually use periodic boundary conditions to minimize corrections from finite cell boundaries but the long range of the Coulomb interactions generates significant contributions from distant periodic images of the simulation cell, usually calculated by Ewald sum techniques. This can add significant overhead to computer simulations and hampers the development of intuitive local pictures and simple analytic theory. In this paper, we present a general framework based on local molecular field theory to accurately determine the contributions from long-ranged Coulomb interactions to the potential of mean force between ionic or apolar hydrophobic solutes in dilute aqueous solutions described by standard classical point charge water models. The simplest approximation leads to a short solvent (SS) model, with truncated solvent–solvent and solute–solvent Coulomb interactions and long-ranged but screened Coulomb interactions only between charged solutes. The SS model accurately describes the interplay between strong short-ranged solute core interactions, local hydrogen-bond configurations, and long-ranged dielectric screening of distant charges, competing effects that are difficult to capture in standard implicit solvent models.

Alchemical free energy calculations and umbrella sampling with local molecular field theory

Understanding the thermodynamic driving forces underlying any chemical process requires a description of the underlying free energy surface. However, computation of free energies is difficult, often requiring advanced sampling techniques. Moreover, these computations can be further complicated by the evaluation of any long-ranged interactions in the system of interest, such as Coulomb interactions in charged and polar media. Local molecular field theory is a promising approach to avoid many of the conceptual and computational difficulties associated with long-ranged interactions. We present frameworks for performing alchemical free energy calculations and non-Boltzmann sampling with local molecular field theory. We demonstrate that local molecular field theory can be used to perform these free energy calculations with accuracy comparable to traditional methodologies while eliminating the need for explicit treatment of long-ranged interactions in simulations.