Polarizable molecular interactions in condensed phase and their equivalent nonpolarizable models

Abstract

Earlier, using phenomenological approach, we showed that in some cases polarizable models of condensed phase systems can be reduced to nonpolarizable equivalent models with scaled charges. Examples of such systems include ionic liquids, TIPnP-type models of water, protein force fields, and others, where interactions and dynamics of inherently polarizable species can be accurately described by nonpolarizable models. To describe electrostatic interactions, the effective charges of simple ionic liquids are obtained by scaling the actual charges of ions by a factor of 1/sqrt(eps_el), which is due to electronic polarization screening effect; the scaling factor of neutral species is more complicated. Here, using several theoretical models, we examine how exactly the scaling factors appear in theory, and how, and under what conditions, polarizable Hamiltonians are reduced to nonpolarizable ones. These models allow one to trace the origin of the scaling factors, determine their values, and obtain important insights on the nature of polarizable interactions in condensed matter systems.

arXiv comment43 pages, 3 figures

References in corpus (2)

• Accounting for electronic polarization in nonpolarizable force fields
• Polarizable Mean-Field Model of Water for Biological Simulations with Amber and Charmm force fields

Cited by in corpus (8)

• A force field of Li${}^{+}$ , Na${}^{+}$ , K${}^{+}$, Mg${}^{2+}$, Ca${}^{2+}$, Cl${}^{-}$, and SO${}_4^{2-}$ in aqueous solution based on the TIP4P/2005 water model and scaled charges for the ions
• The Madrid-2019 force field for electrolytes in water using TIP4P/2005 and scaled charges: extension to the ions F${}^{-}$, Br${}^{-}$, I${}^{-}$, Rb${}^{+}$, Cs${}^{+}$
• Scaled charges for ions: an improvement but not the final word for modeling electrolytes in water
• Water: one molecule, two surfaces, one mistake
• Computation of Electrical Conductivities of Aqueous Electrolyte Solutions: Two Surfaces , One Property
• Structural and Transport Properties of Li/S Battery Electrolytes: Role of the Polysulfide Species
• Towards Automated Benchmarking of Atomistic Forcefields: Neat Liquid Densities and Static Dielectric Constants from the ThermoML Data Archive
• A comparison of classical interatomic potentials applied to highly concentrated aqueous lithium chloride solutions