Structure of ionic liquids and concentrated electrolytes from a mesoscopic theory
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, , satisfies the scaling relation , where is the Debye screening length and 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 for different ranges of . The experimentally found scaling holds for , and we find n=3 for the same range of the reduced Debye length. For smaller , 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. is proportional to the density of ions) when the variance of the local charge density is large, and 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