Accurate Thermodynamics for Short-Ranged Truncations of Coulomb Interactions in Site-Site Molecular Models

Abstract

Coulomb interactions are present in a wide variety of all-atom force fields. Spherical truncations of these interactions permit fast simulations but are problematic due to their incorrect thermodynamics. Herein we demonstrate that simple analytical corrections for the thermodynamics of uniform truncated systems are possible. In particular results for the SPC/E water model treated with spherically-truncated Coulomb interactions suggested by local molecular field theory [Proc. Nat. Acad. Sci. USA 105, 19136 (2008)] are presented. We extend results developed by Chandler [J. Chem. Phys. 65, 2925 (1976)] so that we may treat the thermodynamics of mixtures of flexible charged and uncharged molecules simulated with spherical truncations. We show that the energy and pressure of spherically-truncated bulk SPC/E water are easily corrected using exact second-moment-like conditions on long-ranged structure. Furthermore, applying the pressure correction as an external pressure removes the density errors observed by other research groups in NPT simulations of spherically-truncated bulk species.

References in corpus (5)

• Local molecular field theory for effective attractions between like charged objects in systems with strong Coulomb interactions
• Interplay of local hydrogen-bonding and long-ranged dipolar forces in simulations of confined water
• Local molecular field theory for the treatment of electrostatics
• Attraction Between Like-Charged Walls: Short-Ranged Simulations Using Local Molecular Field Theory
• A new approach for efficient simulation of Coulomb interactions in ionic fluids

Cited by in corpus (10)

• Self-Consistent Determination of Long-Range Electrostatics in Neural Network Potentials
• Dissecting Hydrophobic Hydration and Association
• Deconstructing classical water models at interfaces and in bulk
• Dielectric response with short-ranged electrostatics
• On the efficient and accurate short-ranged simulations of uniform polar molecular liquids
• Learning classical density functionals for ionic fluids
• The Symmetry-Preserving Mean Field Condition for Electrostatic Correlations in Bulk
• A classical density functional theory for solvation across length scales
• The Influence of Distant Boundaries on the Solvation of Charged Particles
• Molecular theory and the effects of solute attractive forces on hydrophobic interactions