English

Structure of ionic liquids and concentrated electrolytes from a mesoscopic theory

Statistical Mechanics 2022-11-07 v1

Abstract

Recently, underscreening in concentrated electrolytes was discovered in experiments and confirmed in simulations and theory. It was found that the correlation length of the charge-charge correlations, λs\lambda_s, satisfies the scaling relation λs/λD(a/λD)n\lambda_s/\lambda_D\sim (a/\lambda_D)^n, where λD\lambda_D is the Debye screening length and aa is the ionic diameter. However, different values of n were found in different studies. In this work we solve this puzzle within the mesocopic theory that yielded n=3 in agreement with experiments, but only very high densities of ions were considered [A. Ciach A. and O. Patsahan, {\it J.Phys.: Condens. Matter} {\textbf 33}, 37LT01 (2021)]. Here we apply the theory to a broader range of density of ions and find that different values of n in the above scaling can yield a fair approximation for λs/λD\lambda_s/\lambda_D for different ranges of a/λDa/\lambda_D. The experimentally found scaling holds for 2<a/λD<42 <a/\lambda_D<4, and we find n=3 for the same range of the reduced Debye length. For smaller a/λDa/\lambda_D, we find n=2 obtained earlier in several simulation and theoretical studies, and still closer to the Kirkwood line we obtain n=1.5 that was also predicted in different works. It follows from our theory that n=3 (i.e. λs\lambda_s is proportional to the density of ions) when the variance of the local charge density is large, and λs\lambda_s is proportional to this variance times the Bjerrum length. Detailed derivation of the theory is presented.

Keywords

Cite

@article{arxiv.2211.02367,
  title  = {Structure of ionic liquids and concentrated electrolytes from a mesoscopic theory},
  author = {A. Ciach and O. Patsahan},
  journal= {arXiv preprint arXiv:2211.02367},
  year   = {2022}
}

Comments

23 pages, 11 figures