Electrical noise in electrolytes: a theoretical perspective

TL;DR

This paper provides a theoretical framework for understanding electrical fluctuations in electrolytes, linking experimental observations to microscopic ion and solvent dynamics through the charge-charge dynamic structure factor.

Contribution

It unifies various experimental probes of electrolyte fluctuations by emphasizing the role of the charge-charge dynamic structure factor and evaluates the Poisson-Nernst-Planck theory's effectiveness.

Findings

Charge-charge dynamic structure factor is central to electrolyte fluctuations.

Simulations of NaCl solutions reveal limitations of standard PNP theory.

Ions and water contributions to charge fluctuations are distinguished.

Abstract

Seemingly unrelated experiments such as electrolyte transport through nanotubes, nano-scale electrochemistry, NMR relaxometry and Surface Force Balance measurements, all probe electrical fluctuations: of the electric current, the charge and polarization, the field gradient (for quadrupolar nuclei) and the coupled mass/charge densities. The fluctuations of such various observables arise from the same underlying microscopic dynamics of the ions and solvent molecules. In principle, the relevant length and time scales of these dynamics are encoded in the dynamic structure factors. However modelling the latter for frequencies and wavevectors spanning many orders of magnitude remains a great challenge to interpret the experiments in terms of physical process such as solvation dynamics, diffusion, electrostatic and hydrodynamic interactions between ions, interactions with solid surfaces, etc. Here, we highlight the central role of the charge-charge dynamic structure factor in the fluctuations of electrical observables in electrolytes and offer a unifying perspective over a variety of complementary experiments. We further analyze this quantity in the special case of an aqueous NaCl electrolyte, using simulations with explicit ions and an explicit or implicit solvent. We discuss the ability of the standard Poisson-Nernst-Planck theory to capture the simulation results, and how the predictions can be improved. We finally discuss the contributions of ions and water to the total charge fluctuations. This work illustrates an ongoing effort towards a comprehensive understanding of electrical fluctuations in bulk and confined electrolytes, in order to enable experimentalists to decipher the microscopic properties encoded in the measured electrical noise.