Mesoscale modeling of complex binary fluid mixtures: towards an atomistic foundation of effective potentials

• Published in: The Journal of chemical physics Vol. 124; no. 7; p. 74105
• Main Authors: Silbermann, Jörg R, Klapp, Sabine H L, Schoen, Martin, Chennamsetty, Naresh, Bock, Henry, Gubbins, Keith E
• Format: Journal Article
• Language: English
• Published: United States 21.02.2006
• ISSN: 0021-9606
• DOI: 10.1063/1.2161207

This paper is devoted to equilibrium molecular-dynamics (MD) simulations of a fully atomistic model of binary mixtures of water (component 1) and ethanol (component 2). We investigate ways to extract from these simulations effective, pairwise additive potentials suitable to describe the interactions between coarse-grained molecules (i.e., beads) in corresponding mesoscale dissipative particle-dynamics simulations. The fully atomistic model employed in MD simulations is mapped onto an implicit water model, where the internal degrees of freedom of ethanol and all the degrees of freedom of water are integrated out. This gives us an effective one-component system consisting only of ethanol beads. The effective interaction potential between a pair of ethanol beads, Phi(R), is approximated at three levels of sophistication. At the lowest one, we approximate Phi(R) by the potential of mean force between the centers of mass of two ethanol beads calculated in the fully atomistic MD simulations; at the second level, we take Phi(R) to be the potential linked to total and direct correlation functions in the hypernetted-chain closure of the Ornstein-Zernike equation. At the third level we approximate Phi(R) numerically by improving it iteratively through the Boltzmann inversion scheme. Our results indicate that the level-one approach works only at the lowest (8 wt %) concentration; the level-two approach works only up to intermediate ethanol concentrations (ca. 50 wt %). Only the Boltzmann inversion scheme works for all, up to the highest concentration considered (70 wt %).