A correlation-hole approach to the electric double layer with counter-ions only

ABSTRACT

We study a classical system of identically charged counter-ions near a planar wall carrying a uniform surface charge density. The equilibrium statistical mechanics of the system depends on a single dimensionless coupling parameter. A new self-consistent theory of the correlation-hole type is proposed which leads to a modified Poisson–Boltzmann integral equation for the density profile, convenient for analytical progress and straightforward to solve numerically. The exact density profiles are recovered in the limits of weak and strong couplings. In contrast to previous theoretical attempts of the test-charge family, the density profiles fulfil the contact-value theorem at all values of the coupling constant and exhibit the mean-field decay at asymptotically large distances from the wall, as expected. We furthermore show that the density corrections at large couplings exhibit the proper dependence on coupling parameter and distance to the charged wall. The numerical results for intermediate values of the coupling provide accurate density profiles which are in good agreement with those obtained by Monte Carlo simulations. The crossover to mean-field behaviour at large distance is studied in detail.

GRAPHICAL ABSTRACT

Keywords:

• statistical mechanics
• electric-double layer
• correlation-hole
• planar interfaces

Disclosure statement

No potential conflict of interest was reported by the authors.

Notes

1 Yet, as alluded to above, reaching the z-range where the log correction is relevant becomes in practice impossible when increasing Ξ. For instance, we would need for and already for . Thus, the log correction can only be probed at .

Additional information

Funding

It is a pleasure to dedicate this work to Daan Frenkel as a tribute to his exceptional human and scientific qualities (depth, vista, swiftness), be it as a mentor or a colleague. To counter-quote Churchill, Daan is a modest man, who does not have much to be modest about. The support received from VEGA Grant No. 2/0003/18 is acknowledged. The work was funded by the European Union's Horizon 2020 research and innovation programme under ETN grant 674979-NANOTRANS. M.T. acknowledges financial support by the Swedish Research Council (621-2014-4387).