%0 Journal Article %1 reinauer24 %A Reinauer, Alexander %A Kondrat, Svyatoslav %A Holm, Christian %C United States %D 2024 %J The Journal of chemical physics %K EXC2075 PN3 PN3-3 curated %N 10 %P 104101-- %R 10.1063/5.0226959 %T Electrolytes in conducting nanopores: Revisiting constant charge and constant potential simulations %U https://pubmed.ncbi.nlm.nih.gov/39248380 %V 161 %X Simulating electrolyte-electrode systems poses challenges due to the need to account for the electrode's response to ion movements in order to maintain a constant electrode potential, which slows down the simulations. To circumvent this, computationally more efficient constant charge (CC) simulations are sometimes employed. However, the accuracy of CC simulations in capturing the behavior of electrolyte-electrode systems remains unclear, especially for microporous electrodes. Herein, we consider electrolyte-filled slit nanopores and systematically analyze the in-pore ion structure and diffusivity using CC and constant potential simulations. Our results indicate that CC simulations provide comparable pore occupancies at high bulk ion densities and for highly charged pores, but they fail to accurately describe the ion structure and dynamics, particularly in quasi-2D (single-layer) pores and at low ion densities. We attribute these results to the superionic state emerging in conducting nanoconfinement and its interplay with excluded volume interactions.

@article{reinauer24, abstract = {Simulating electrolyte-electrode systems poses challenges due to the need to account for the electrode's response to ion movements in order to maintain a constant electrode potential, which slows down the simulations. To circumvent this, computationally more efficient constant charge (CC) simulations are sometimes employed. However, the accuracy of CC simulations in capturing the behavior of electrolyte-electrode systems remains unclear, especially for microporous electrodes. Herein, we consider electrolyte-filled slit nanopores and systematically analyze the in-pore ion structure and diffusivity using CC and constant potential simulations. Our results indicate that CC simulations provide comparable pore occupancies at high bulk ion densities and for highly charged pores, but they fail to accurately describe the ion structure and dynamics, particularly in quasi-2D (single-layer) pores and at low ion densities. We attribute these results to the superionic state emerging in conducting nanoconfinement and its interplay with excluded volume interactions.}, added-at = {2024-09-12T10:07:34.000+0200}, address = {United States}, author = {Reinauer, Alexander and Kondrat, Svyatoslav and Holm, Christian}, biburl = {https://puma.ub.uni-stuttgart.de/bibtex/2cf84eb5764cc1a803a303492eff66c13/simtech}, comment = {39248380[pmid]}, description = {Electrolytes in conducting nanopores: Revisiting constant charge and constant potential simulations - PubMed}, doi = {10.1063/5.0226959}, interhash = {0379720d52733037fed53f62ebb46e90}, intrahash = {cf84eb5764cc1a803a303492eff66c13}, issn = {10897690}, journal = {The Journal of chemical physics}, keywords = {EXC2075 PN3 PN3-3 curated}, month = sep, number = 10, pages = {104101--}, timestamp = {2025-02-28T16:08:06.000+0100}, title = {Electrolytes in conducting nanopores: Revisiting constant charge and constant potential simulations}, url = {https://pubmed.ncbi.nlm.nih.gov/39248380}, volume = 161, year = 2024 }