@article{22769f9449ce4b62b8fc1c313448b3e6,
title = "Ion correlations drive charge overscreening and heterogeneous nucleation at solid-aqueous electrolyte interfaces",
abstract = "Classical electrical double layer (EDL) models are foundational to the representation of atomistic structure and reactivity at charged interfaces. An important limitation to these models is their dependence on a mean-field approximation that is strictly valid for dilute aqueous solutions. Theoretical efforts to overcome this limitation are severely impeded by the lack of visualization of the structure over a wide range of ion concentration. Here, we report the salinity-dependent evolution of EDL structure at negatively charged mica-water interfaces, revealing transition from the Langmuir-type charge compensation in dilute salt solutions to nonclassical charge overscreening in highly concentrated solutions. The EDL structure in this overcharging regime is characterized by the development of both lateral positional correlation between adsorbed ions and vertical layering of alternating cations and anions reminiscent of the structures of strongly correlated ionic liquids. These EDL ions can spontaneously grow into nanocrystalline nuclei of ionic compounds at threshold ion concentrations that are significantly lower than the bulk solubility limit. These results shed light on the impact of ion cooperativity that drives heterogeneous nonclassical behaviors of the EDL in highsalinity conditions.",
keywords = "Adsorption, EDL, Molecular dynamics, Salinity, X-ray reflectivity",
author = "Lee, {Sang Soo} and Ayumi Koishi and Bourg, {Ian C.} and Paul Fenter",
note = "Funding Information: ACKNOWLEDGMENTS. This work was supported by the US Department of Energy Offices of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences under Contracts DE-AC02-06CH11357 to UChicago Argonne, LLC as operator of Argonne National Laboratory (Argonne) (to S.S.L. and P.F. for measurements and analysis of XR data) and DE-SC0018419 to Princeton University (to A.K. and I.C.B. for computational simulations and data analysis). The X-ray data were collected at the beamline 33-ID-D, Advanced Photon Source. Use of the Advanced Photon Source was supported by the US Department of Energy Offices of Science and Basic Energy Sciences under Contract DE-AC02-06CH11357 to UChicago Argonne, LLC as operator of Argonne National Laboratory. MD simulations were performed using resources at NERSC, which is supported by the US Department of Energy Office of Science under Award DE-AC02-05CH11231. The submitted manuscript has been created by UChicago Argonne, LLC, operator of Argonne. Argonne, a US Department of Energy Office of Science laboratory, is operated under Contract DE-AC02-06CH11357. The US Government retains for itself, and others acting on its behalf, a paid-up nonexclusive, irrevocable worldwide license in said article to reproduce, prepare derivative works, distribute copies to the public, and perform publicly and display publicly, by or on behalf of the Government. Publisher Copyright: {\textcopyright} 2021 National Academy of Sciences. All rights reserved.",
year = "2021",
month = aug,
day = "10",
doi = "10.1073/pnas.2105154118",
language = "English (US)",
volume = "118",
journal = "Proceedings of the National Academy of Sciences of the United States of America",
issn = "0027-8424",
publisher = "National Academy of Sciences",
number = "32",
}