Electric-field-induced oscillations in ionic fluids: a unified formulation of modified Poisson-Nernst-Planck models and its relevance to correlation function analysis
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arXiv
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| Format: | Preprint |
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2022
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| _version_ | 1866917891671064576 |
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| author | Frusawa, Hiroshi |
| author_facet | Frusawa, Hiroshi |
| contents | We theoretically investigate an electric-field-driven system of charged spheres as a primitive model of concentrated electrolytes under an applied electric field. First, we provide a unified formulation for the stochastic charge and density dynamics of the electric-field-driven primitive model using the stochastic density functional theory (DFT). The stochastic DFT integrates various frameworks of the equilibrium and dynamic DFTs, the liquid state theory, and the field-theoretic approach, which allows us to justify in a unified manner various modifications previously made for the Poisson-Nernst-Planck model. Next, we consider stationary density-density and charge-charge correlation functions of the primitive model with a static electric field. We focus on an electric-field-induced synchronization between the emergence of density and charge oscillations, or the crossover from monotonic to oscillatory decay of density-density and charge-charge correlations. The correlation function analysis demonstrates the appearance of stripe states formed by segregation bands perpendicular to the external field. We also predict the following: (i) the electric-field-induced crossover occurs prior to the conventional Kirkwood crossover without an applied electric field, and (ii) the ion concentration dependence of the decay lengths at the electric-field-induced crossovers bears a similarity to the underscreening behavior found by simulation and theoretical studies on the oscillatory decay length in equilibrium. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2203_15428 |
| institution | arXiv |
| publishDate | 2022 |
| record_format | arxiv |
| spellingShingle | Electric-field-induced oscillations in ionic fluids: a unified formulation of modified Poisson-Nernst-Planck models and its relevance to correlation function analysis Frusawa, Hiroshi Soft Condensed Matter Materials Science Statistical Mechanics Chemical Physics We theoretically investigate an electric-field-driven system of charged spheres as a primitive model of concentrated electrolytes under an applied electric field. First, we provide a unified formulation for the stochastic charge and density dynamics of the electric-field-driven primitive model using the stochastic density functional theory (DFT). The stochastic DFT integrates various frameworks of the equilibrium and dynamic DFTs, the liquid state theory, and the field-theoretic approach, which allows us to justify in a unified manner various modifications previously made for the Poisson-Nernst-Planck model. Next, we consider stationary density-density and charge-charge correlation functions of the primitive model with a static electric field. We focus on an electric-field-induced synchronization between the emergence of density and charge oscillations, or the crossover from monotonic to oscillatory decay of density-density and charge-charge correlations. The correlation function analysis demonstrates the appearance of stripe states formed by segregation bands perpendicular to the external field. We also predict the following: (i) the electric-field-induced crossover occurs prior to the conventional Kirkwood crossover without an applied electric field, and (ii) the ion concentration dependence of the decay lengths at the electric-field-induced crossovers bears a similarity to the underscreening behavior found by simulation and theoretical studies on the oscillatory decay length in equilibrium. |
| title | Electric-field-induced oscillations in ionic fluids: a unified formulation of modified Poisson-Nernst-Planck models and its relevance to correlation function analysis |
| topic | Soft Condensed Matter Materials Science Statistical Mechanics Chemical Physics |
| url | https://arxiv.org/abs/2203.15428 |