Molecular dynamics simulations of aqueous RbBr-solutions over the entire solubility range at room temperature

Harsányi, Ildikó; Pusztai, László; Soetens, Jean-Christophe; Bopp, P.

doi:10.1016/j.molliq.2006.08.005

Cited by 15 publications

(13 citation statements)

References 17 publications

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“…Interestingly, this rattling motion is more markedly observed for Br – than for the lightest Cl – , something to be attributable to the fact that this latter anion is more strongly hydrated than the former. Besides, the main effect of water addition is a progressive smoothing out of the VACF until the pure water value is recoveredin agreement to previously reported results. , Contrarily to what happened with the collision time, an increase in the chain length leads to a less oscillatory behavior of the VACF in the case of the first compounds.…”

Section: Resultssupporting

confidence: 92%

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Molecular Dynamics Simulation of the Structure and Dynamics of Water–1-Alkyl-3-methylimidazolium Ionic Liquid Mixtures

et al. 2011

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We have performed extensive molecular dynamic simulations to analyze the influence of cation and anion natures, and of water concentration, on the structure and dynamics of water-1-alkyl-3-methylimidazolium ionic liquid mixtures. The dependence on water concentration of the radial distribution functions, coordination numbers, and hydrogen bonding degree between the different species has been systematically analyzed for different lengths of the cation alkyl chain (alkyl = ethyl, butyl, hexyl, and octyl) and several counterions. These include two halogens of different sizes and positions in Hoffmeister series, Cl(-) and Br(-), and the highly hydrophobic inorganic anion PF(6)(-) throughout its whole solubility regime. The formation of water clusters in the mixture has been verified, and the influences of both anion hydrophobicity and cation chain length on the structure and size of these clusters have been analyzed. The water cluster size is shown to be relatively independent of the cation chain length, but strongly dependent on the hydrophobicity of the anion, which also determines critically the network formation of water and therefore the miscibility of the ionic liquid. The greater influence of the anion relative to the cation one is seen to be reflected in all the analyzed physical properties. Finally, single-particle dynamics in IL-water mixtures is considered, obtaining the self-diffusion coefficients and the velocity autocorrelation functions of water molecules in the mixture, and analyzing the effect of cation, anion, and water concentration on the duration of the ballistic regime and on the time of transition to the diffusive regime. Complex non-Markovian behavior was detected at intermediate times within an interval progressively shorter as water concentration increases.

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Section: Resultssupporting

confidence: 92%

“…Besides, the main effect of water addition is a progressive smoothing out of the VACF until the pure water value is recovered-in agreement to previously reported results. 59,60 Contrarily to what happened with the collision time, an increase in the chain length leads to a less oscillatory behavior of the VACF in the case of the first compounds.…”

Section: Articlementioning

confidence: 97%

Molecular Dynamics Simulation of the Structure and Dynamics of Water–1-Alkyl-3-methylimidazolium Ionic Liquid Mixtures

et al. 2011

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“…This is because the size of the simulation box is not important since no Fourier transform is carried out and there is no difficulty with rigid water models, for which approximations concerning the intramolecular part would otherwise be necessary. 25 In the RMC calculations, 2000 flexible water molecules (i.e., 6000 atoms) were employed at the experimental atomic number density of 0.099 atoms per Å -3 . According to the protocol described in ref 3, the experimental tssf of heavy water 26 along with the three (O-O, O-H, and H-H) prdf's from an MD simulation of bulk POL3 water 4 were used as input data for RMC.…”

Section: Methodsmentioning

confidence: 99%

“…Note that this approach, while also being more instructive, is easier to perform than combining prdf’s from MD simulations to provide the tssf’s. This is because the size of the simulation box is not important since no Fourier transform is carried out and there is no difficulty with rigid water models, for which approximations concerning the intramolecular part would otherwise be necessary …”

Section: Methodsmentioning

confidence: 99%

Benchmarking Polarizable Molecular Dynamics Simulations of Aqueous Sodium Hydroxide by Diffraction Measurements

et al. 2009

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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.

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“…At room temperature, and for these rather low concentrations, all the ions are dissolved. [23][24][25] …”

Section: Sample Preparationmentioning

confidence: 99%

Influence of monovalent ions on density fluctuations in hydrothermal aqueous solutions by small angle X-ray scattering

Cadoux

Hazemann

Testemale

et al. 2012

The Journal of Chemical Physics

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Synchrotron small angle X-ray scattering measurements on water and alkaline bromine aqueous solutions (XBr, with X = Li, Rb, or Cs) were carried out from ambient to supercritical conditions. The temperature was increased from 300 to 750 K along several isobars between 24 and 35 MPa. The correlation length and the structure factor were extracted from the data following the Ornstein-Zernike formalism. We obtained experimental evidence of the shift of the critical point and isochore and their dependence on the ions concentration (0.33 mol/kg and 1.0 mol/kg). We also observed that the size of the density fluctuations and the structure factor increase with the presence of the ions and that this effect is positively correlated with the atomic number of the cation. These behaviors were compared with ZnBr(2) and NaCl systems from the literature.

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Molecular dynamics simulations of aqueous RbBr-solutions over the entire solubility range at room temperature

Cited by 15 publications

References 17 publications

Molecular Dynamics Simulation of the Structure and Dynamics of Water–1-Alkyl-3-methylimidazolium Ionic Liquid Mixtures

Molecular Dynamics Simulation of the Structure and Dynamics of Water–1-Alkyl-3-methylimidazolium Ionic Liquid Mixtures

Benchmarking Polarizable Molecular Dynamics Simulations of Aqueous Sodium Hydroxide by Diffraction Measurements

Influence of monovalent ions on density fluctuations in hydrothermal aqueous solutions by small angle X-ray scattering

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