Alexander Reinauer, Svyatoslav Kondrat, Christian Holm
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引用次数: 0
摘要
模拟电解质-电极系统是一项挑战,因为需要考虑电极对离子运动的反应,以保持恒定的电极电位,这就减慢了模拟速度。为了避免这种情况,有时会采用计算效率更高的恒电荷(CC)模拟。然而,CC 模拟在捕捉电解质电极系统行为方面的准确性仍不明确,尤其是对于微孔电极。在此,我们考虑了充满电解质的狭缝纳米孔,并使用 CC 和恒电位模拟系统分析了孔内离子结构和扩散性。我们的研究结果表明,CC 模拟可提供高体离子密度和高电荷孔隙的可比孔隙占有率,但无法准确描述离子结构和动力学,尤其是在准二维(单层)孔隙和低离子密度时。我们将这些结果归因于传导纳米孔隙中出现的超离子状态及其与排除体积相互作用的相互作用。
Electrolytes in conducting nanopores: Revisiting constant charge and constant potential simulations.
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.
期刊介绍:
The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance.
Topical coverage includes:
Theoretical Methods and Algorithms
Advanced Experimental Techniques
Atoms, Molecules, and Clusters
Liquids, Glasses, and Crystals
Surfaces, Interfaces, and Materials
Polymers and Soft Matter
Biological Molecules and Networks.