Correlating Metal-Water Interactions and Double-Layer Capacitance at Gold and Silver: Revisit of Single-Crystal Experiments Using a Unified Theoretical Model

IF 5.8 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Chemical Theory and Computation Pub Date : 2026-10-20 DOI:10.1021/acs.jctc.6c01350

Er-Fei Zhen,Chen-Yu Zhang,Yan-Xia Chen

{"title":"Correlating Metal-Water Interactions and Double-Layer Capacitance at Gold and Silver: Revisit of Single-Crystal Experiments Using a Unified Theoretical Model","authors":"Er-Fei Zhen,Chen-Yu Zhang,Yan-Xia Chen","doi":"10.1021/acs.jctc.6c01350","DOIUrl":null,"url":null,"abstract":"We quantify how metal identity and crystallographic orientation shape the electrical double layer (EDL) and differential capacitance (Cdl) in weakly adsorbing electrolytes. The concentration-dependent Cdl curves of Ag(110), Ag(100), Ag(111), and Au(110) in aqueous KPF6, are quantitatively analyzed using the density-potential functional theory (DPFT). The comparative analysis results in four key findings. First, in accordance with conventional understanding, Cdl is dominated by the diffuse layer and is identical for Ag and Au electrodes near their respective potential of zero free charge (pzfc) at the same low electrolyte concentrations. Second, the Cdl sequence of Ag(110)>Ag(100)>Ag(111) at their pzfc at the same higher electrolyte concentration is attributed to facet-dependent water adsorption. Third, under same solution conditions, Ag(110) shows a higher Cdl peak and smaller peak-to-peak spacing than Au(110), reflecting differences in short-range metal-water interaction, metal-ion interaction and electron spillover at the metal surface. Fourth, partial desolvation under strong interfacial fields further reshapes the ionic distribution and lifts the Cdl curves away from the pzfc. Overall, these results map macroscopic capacitance fingerprints onto microscopic EDL structure within a unified DPFT framework.","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":"73 1","pages":""},"PeriodicalIF":5.8000,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Theory and Computation","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.jctc.6c01350","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}

引用次数: 0

Abstract

We quantify how metal identity and crystallographic orientation shape the electrical double layer (EDL) and differential capacitance (Cdl) in weakly adsorbing electrolytes. The concentration-dependent Cdl curves of Ag(110), Ag(100), Ag(111), and Au(110) in aqueous KPF6, are quantitatively analyzed using the density-potential functional theory (DPFT). The comparative analysis results in four key findings. First, in accordance with conventional understanding, Cdl is dominated by the diffuse layer and is identical for Ag and Au electrodes near their respective potential of zero free charge (pzfc) at the same low electrolyte concentrations. Second, the Cdl sequence of Ag(110)>Ag(100)>Ag(111) at their pzfc at the same higher electrolyte concentration is attributed to facet-dependent water adsorption. Third, under same solution conditions, Ag(110) shows a higher Cdl peak and smaller peak-to-peak spacing than Au(110), reflecting differences in short-range metal-water interaction, metal-ion interaction and electron spillover at the metal surface. Fourth, partial desolvation under strong interfacial fields further reshapes the ionic distribution and lifts the Cdl curves away from the pzfc. Overall, these results map macroscopic capacitance fingerprints onto microscopic EDL structure within a unified DPFT framework.

Abstract Image

查看原文本刊更多论文

金和银的金属-水相互作用和双层电容：用统一理论模型重新审视单晶实验

我们量化了金属同一性和晶体取向如何在弱吸附电解质中形成双电层（EDL）和差分电容（Cdl）。利用密度势泛函理论（DPFT）定量分析了水相KPF6中Ag（110）、Ag（100）、Ag（111）和Au（110）的浓度依赖性Cdl曲线。对比分析得出了四个关键结论。首先，根据传统的理解，Cdl由扩散层主导，并且在相同的低电解质浓度下，Ag和Au电极在各自的零自由电荷电位（pzfc）附近是相同的。其次，在相同的较高电解质浓度下，Ag(110)>Ag(100)>Ag（111）的pzfc的Cdl序列归因于面依赖的水吸附。第三，在相同的溶液条件下，Ag（110）的Cdl峰比Au（110）高，峰间距也比Au（110）小，反映了金属-水相互作用、金属-离子相互作用和金属表面电子溢出的短程差异。第四，强界面场作用下的部分脱溶进一步改变了离子分布，使Cdl曲线远离pzfc。总的来说，这些结果将宏观电容指纹映射到统一DPFT框架内的微观EDL结构上。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Journal of Chemical Theory and Computation 化学-物理：原子、分子和化学物理

CiteScore

9.90

自引率

16.40%

发文量

568

审稿时长

1 months

期刊介绍： The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.