Moment-Tensor-Based Constant-Potential Modeling of Electrical Double Layers
Constant-potential molecular dynamics (MD) simulations are indispensable for understanding the capacitance, structure, and dynamics of electrical double layers (EDLs) at the atomistic level. However, the classical constant-potential method, relying on the so-called 'floating charges' to keep electrode equipotential, overlooks quantum effects on the electrode and always underestimates EDL capacitance for typical electrochemical systems featuring metal electrodes in aqueous electrolytes. Here, we propose a universal theoretical framework as moment-tensor-based constant potential method (mCPM) to capture electronic structure variations with electric moments. For EDLs at Au(111) electrodes, mCPM-based MD reveals bell-shaped capacitance curves in magnitude and shape both quantitatively consistent with experiments. It further unveils the potential-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 identifies geometry dependence of two time scales during EDL formation..
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Preprint| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
arXiv.org - (2024) vom: 30. Jan. Zur Gesamtaufnahme - year:2024 |
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| Sprache: |
Englisch |
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| Beteiligte Personen: |
Wang, Zhenxiang [VerfasserIn] |
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| Links: |
Volltext [kostenfrei] |
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| Themen: |
530 |
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| PPN (Katalog-ID): |
XAR042326052 |
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| 100 | 1 | |a Wang, Zhenxiang |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Moment-Tensor-Based Constant-Potential Modeling of Electrical Double Layers |
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| 520 | |a Constant-potential molecular dynamics (MD) simulations are indispensable for understanding the capacitance, structure, and dynamics of electrical double layers (EDLs) at the atomistic level. However, the classical constant-potential method, relying on the so-called 'floating charges' to keep electrode equipotential, overlooks quantum effects on the electrode and always underestimates EDL capacitance for typical electrochemical systems featuring metal electrodes in aqueous electrolytes. Here, we propose a universal theoretical framework as moment-tensor-based constant potential method (mCPM) to capture electronic structure variations with electric moments. For EDLs at Au(111) electrodes, mCPM-based MD reveals bell-shaped capacitance curves in magnitude and shape both quantitatively consistent with experiments. It further unveils the potential-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 identifies geometry dependence of two time scales during EDL formation. | ||
| 650 | 4 | |a Physics - Chemical Physics |7 (dpeaa)DE-84 | |
| 650 | 4 | |a Physics - Mesoscopic Systems and Quantum Hall Effect |7 (dpeaa)DE-84 | |
| 650 | 4 | |a 530 |7 (dpeaa)DE-84 | |
| 700 | 1 | |a Chen, Ming |4 aut | |
| 700 | 1 | |a Wu, Jiedu |4 aut | |
| 700 | 1 | |a Ji, Xiangyu |4 aut | |
| 700 | 1 | |a Zeng, Liang |4 aut | |
| 700 | 1 | |a Peng, Jiaxing |4 aut | |
| 700 | 1 | |a Yan, Jiawei |4 aut | |
| 700 | 1 | |a Kornyshev, Alexei A. |4 aut | |
| 700 | 1 | |a Mao, Bingwei |4 aut | |
| 700 | 1 | |a Feng, Guang |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t arXiv.org |g (2024) vom: 30. Jan. |
| 773 | 1 | 8 | |g year:2024 |g day:30 |g month:01 |
| 856 | 4 | 0 | |u https://arxiv.org/abs/2401.17145 |z kostenfrei |3 Volltext |
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