Reaction-field electrostatics in molecular dynamics simulations: development of a conservative scheme compatible with an atomic cutoff

Abstract

In molecular dynamics (MD) simulations of condensed-phase systems, straight-cutoff truncation of the non-bonded interactions is well known to cause cutoff noise and serious artifacts in many simulated properties. These effects can be drastically reduced by applying the truncation based on distances between neutral charge groups (CG) rather than between individual atoms (AT). In addition, the mean effect of the omitted electrostatic interactions beyond the cutoff distance can be reintroduced using the reaction-field (RF) method, where the medium outside the cutoff sphere is approximated as a dielectric continuum of permittivity equal to that of the solvent. The RF scheme is generally applied with CG truncation. This is justified for low solvent permittivities, where the RF correction is small and an AT truncation would lead to severe issues, just as in the straight-cutoff case. However, it is less appropriate for solvents with high permittivities, where the RF correction acts as a physically motivated shifting function, and a CG truncation may in turn lead to artifacts and poorer energy conservation. In this study, we assess the impact of truncation artifacts considering the 57 organic liquids which were used in the calibration of the GROMOS-compatible 2016H66 force field. Combinations of shifting or switching schemes with RF-based electrostatic interactions as well as van der Waals (Lennard-Jones) interactions are then introduced to resolve the issues with AT truncation. These shifting and switching schemes have the following properties: (i) they bring the force but not the potential energy to zero at the cutoff; (ii) as a result, they lead to a modification of the interaction that is comparatively small; (iii) they permit to conduct rigorously conservative simulations; (iv) the energies can easily be corrected back to the unmodified form, either on the fly or in a post-processing step. The mathematical formalism of these schemes is presented in detail, and their validation is performed using the 57 organic liquids.