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Issue 28, 2018
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Density functional theory for charged fluids

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Abstract

An improved density functional theory (DFT) for an inhomogeneous charged system (including electrolyte and/or polyelectrolyte) is proposed based on fundamental measure theory, thermodynamic perturbation theory and mean-spherical approximation. Our DFT combines the existing treatment of hard-sphere contributions using fundamental measure theory (FMT) with a new treatment of the electrostatic correlations for the non-bonded ions and chain connectivity that are approximated by employing a first-order Taylor expansion, with the reference fluid density determined using the technique from Gillespie et al. [D. Gillespie et al., J. Phys.: Condens. Matter, 2002, 14, 12129]. We show that the first-order Taylor expansion for the non-bonded electrostatic correlations yields numerically comparable results to the more involved second-order expansion. Furthermore, we find that the existing treatment of the chain connectivity correlation predicts a spurious layer-by-layer phase at moderately large Bjerrum lengths, which is avoided in our new treatment. These simplifications and improvements should significantly facilitate the implementation and reduce the computational cost.

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Publication details

The article was received on 21 Mar 2018, accepted on 12 Jun 2018 and first published on 13 Jun 2018


Article type: Paper
DOI: 10.1039/C8SM00595H
Citation: Soft Matter, 2018,14, 5878-5887
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    Density functional theory for charged fluids

    J. Jiang, V. V. Ginzburg and Z. Wang, Soft Matter, 2018, 14, 5878
    DOI: 10.1039/C8SM00595H

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