Based on a mean-field description of thermodynamic cyclic voltammograms (CVs), we analyze here in full generality, how CV peak positions and shapes are related to the underlying interface energetics, in particular when also including electrostatic double layer (DL) effects. We show in particular, how non-Nernstian behaviour is related to capacitive DL charging, and how this relates to common adsorbate-centered interpretations such as a changed adsorption energetics due to dipole-field interactions and the electrosorption valency – the number of exchanged electrons upon electrosorption per adsorbate. Using Ag(111) in halide-containing solutions as test case, we demonstrate that DL effects can introduce peak shifts that are already explained by rationalizing the interaction of isolated adsorbates with the interfacial fields, while alterations of the peak shape are mainly driven by the coverage-dependence of the adsorbate dipoles. In addition, we analyze in detail how changing the experimental conditions such as the ion concentrations in the solvent but also of the background electrolyte can affect the CV peaks via their impact on the potential drop in the DL and the DL capacitance, respectively. These results suggest new routes to analyze experimental CVs and use of those for a detailed assessment of the accuracy of atomistic models of electrified interfaces e.g. with and without explicitly treated interfacial solvent and/or approximate implicit solvent models.

基于热力学循环伏安图 (CV) 的平均场描述，我们在这里全面分析了 CV 峰位置和形状如何与底层界面能量相关，特别是当还包括静电双层 (DL) 效应时。我们特别展示了非能斯脱行为如何与电容性 DL 充电相关，以及这与常见的以吸附质为中心的解释如何相关，例如由于偶极场相互作用和电吸附价 - 交换电子的数量而改变的吸附能量每个吸附物的电吸附。使用含卤化物溶液中的 Ag(111) 作为测试案例，我们证明了 DL 效应可以引入峰位移，这已经通过使分离的吸附物与界面场的相互作用合理化来解释，而峰形的改变主要是由吸附质偶极子的覆盖依赖性驱动的。此外，我们详细分析了改变实验条件（例如溶剂中的离子浓度以及背景电解质的浓度）如何分别通过影响 DL 和 DL 电容的电位降来影响 CV 峰。这些结果提出了分析实验 CV 的新途径，并将其用于详细评估带电界面原子模型的准确性，例如，有和没有明确处理的界面溶剂和/或近似隐式溶剂模型。我们详细分析了改变实验条件（例如溶剂中的离子浓度以及背景电解质中的离子浓度）如何分别通过它们对 DL 和 DL 电容的电位降的影响来影响 CV 峰。这些结果提出了分析实验 CV 的新途径，并将其用于详细评估带电界面原子模型的准确性，例如，有和没有明确处理的界面溶剂和/或近似隐式溶剂模型。我们详细分析了改变实验条件（例如溶剂中的离子浓度以及背景电解质中的离子浓度）如何分别通过它们对 DL 和 DL 电容的电位降的影响来影响 CV 峰。这些结果提出了分析实验 CV 的新途径，并将其用于详细评估带电界面原子模型的准确性，例如，有和没有明确处理的界面溶剂和/或近似隐式溶剂模型。