title: Benchmarking polarizable molecular dynamics simulations of aqueous sodium hydroxide by diffraction measurements.
abstract: Results from molecular dynamics simulations of aqueous hydroxide of varying concentrations have been compared with experimental structural data. First, the polarizable POL3 model was verified against neutron scattering using a reverse Monte Carlo fitting procedure. It was found to be competitive with other simple water models and well suited for combining with hydroxide ions. Second, a set of four polarizable models of OH- were developed by fitting against accurate ab initio calculations for small hydroxide-water clusters. All of these models were found to provide similar results that robustly agree with structural data from X-ray scattering. The present force field thus represents a significant improvement over previously tested nonpolarizable potentials. Although it cannot in principle capture proton hopping and can only approximately describe the charge delocalization within the immediate solvent shell around OH-, it provides structural data that are almost entirely consistent with data obtained from scattering experiments.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic and Center for Biomolecules and Complex Molecular Systems, Flemingovo nm. 2, 16610 Prague 6, Czech Republic.
authors.forename: Robert
authors.initials: R
authors.lastname: Vácha
authors.forename: Tunde
authors.initials: T
authors.lastname: Megyes
authors.forename: Imre
authors.initials: I
authors.lastname: Bakó
authors.forename: László
authors.initials: L
authors.lastname: Pusztai
authors.forename: Pavel
authors.initials: P
authors.lastname: Jungwirth
mesh_terms: D000327:Adsorption; D019985:Benchmarking; D003198:Computer Simulation; D006878:Hydroxides / Q000737:chemistry; D008958:Models, Molecular; D033363:Neutron Diffraction; D009821:Oils / Q000737:chemistry; D011789:Quantum Theory; D012972:Sodium Hydroxide / Q000737:chemistry*; D013057:Spectrum Analysis; D013500:Surface Tension; D017186:Titrimetry; D014867:Water / Q000737:chemistry*
chemical_list: D006878:Hydroxides; D009821:Oils; D014867:Water; D012972:Sodium Hydroxide; C031356:hydroxide ion