标题： 电化学界面电子-离子相关性的经典理论：从双层充电到离子吸附的闭环 显示英文标题

标题： Classical theory of electron-ion correlations at electrochemical interfaces: Closing the circuit from double-layer charging to ion adsorption

摘要： 在金属和离子溶液之间的界面形成的双电层（EDL）是各种能源技术的核心。 最近的实验数据挑战了基于平均场Gouy-Chapman-Stern型（GCS）模型的传统EDL充电行为理解。 在本文中，我们提出了一种经典理论，该理论从第一性原理统计力学推导而来，使用图像电荷方法来考虑电子-离子相关效应，并系统地超越了平均场水平。 这种电子-离子相关性在金属表面和电解质离子之间引入了额外的相互作用，显著改变了EDL结构。 我们的理论在稀释电解质溶液和弱带电金属表面的极限下有效，与广泛范围的电极材料和电解质溶剂的实验电容数据实现了定量一致，从而解决了长期以来关于与GCS预测差异起源的问题。 因此，该框架在概念上统一了双层充电和离子吸附（电吸附）过程，这些过程通常被视为不同的现象，但被证明是同一基本静电原理的表现。 显示英文摘要

摘要： The electric double layer (EDL) that forms at the interface between metals and ionic solutions is at the heart of various energy technologies. Recent experimental data have challenged our traditional understanding of the EDL charging behavior, which is based on mean-field Gouy-Chapman-Stern-type (GCS) models. In this article, we present a classical theory for the EDL, derived from first-principles statistical mechanics, that accounts for electron-ion correlation effects using the method of image charges and systematically extends beyond the mean-field level. Such electron-ion correlations introduce an additional interaction between the metal surface and electrolyte ions, significantly altering the EDL structure. Our theory, valid in the limit of dilute electrolyte solutions and weakly charged metal surfaces, achieves quantitative agreement with experimental capacitance data across a wide range of electrode materials and electrolyte solvents, and thus resolves long-standing questions on the origin of discrepancies to GCS predictions. Thereby, the framework conceptually unifies the processes of double-layer charging and ion adsorption (electrosorption), which are typically considered as distinct phenomena, but are shown to be manifestations of the same fundamental electrostatic principles.