Constant-Potential Modeling of Electrical Double Layers Accounting for Electron Spillover.

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Tác giả: Ming Chen, Guang Feng, Xiangyu Ji, Alexei A Kornyshev, Bingwei Mao, Jiaxing Peng, Zhenxiang Wang, Jiedu Wu, Jiawei Yan, Liang Zeng

Ngôn ngữ: eng

Ký hiệu phân loại: 553.453 Tin

Thông tin xuất bản: United States : Physical review letters , 2025

Mô tả vật lý:

Bộ sưu tập: NCBI

ID: 90342

Constant-potential molecular dynamics (MD) simulations are indispensable for understanding the structure, capacitance, and dynamics of electrical double layers (EDLs) at the atomistic level. However, the classical constant-potential method, relying on the so-called "fluctuating charges" to keep electrode equipotential, overlooks quantum effects on the electrode and always underestimates EDL capacitance for typical metal electrode and aqueous electrolyte interfaces. Here, we propose a constant potential method accounting for electron spillover on the outermost nuclei of the electrode. For EDLs at Au(111) electrodes, our MD simulation reveals bell-shaped capacitance curves in magnitude and shape both quantitatively consistent with experiments. It unveils the electrode-polarization-dependent local electric fields, agreeing with experimental observations of redshift vibration of interfacial water under negative polarization and predicting a blueshift under positive polarization, and further identifies geometry dependence of two timescales during charging.
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