Voltage-dependent cluster expansion for electrified solid-liquid interfaces: Application to the electrochemical deposition of transition metals
Voltage-dependent cluster expansion for electrified solid-liquid interfaces: Application to the electrochemical deposition of transition metals
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DOI：
10.1103/physrevb.96.205134
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发表时间：
2017-08
影响因子：
3.7
通讯作者：
Stephen E. Weitzner;I. Dabo
中科院分区：
文献类型：
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作者：
Stephen E. Weitzner;I. Dabo
由于金属-溶液界面的复杂结构和电极极化过程中表面碳化的关键影响，电化学沉积金属单层的详细原子模型具有挑战性。界面电化学平衡的精确模型进一步受到需要包括熵效应以获得精确的表面化学势的挑战。我们提出了一个嵌入式的量子连续模型的界面环境，解决了这些挑战，并研究了欠电位沉积的银的金（100）表面。我们利用这些结果来参数化带电界面的簇膨胀，并通过巨正则蒙特卡罗计算显示，在有限温度电化学条件下建模电沉积金属时，至关重要的需要考虑界面偶极的变化。
The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface elec- trification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parameterize a cluster expansion of the electrified in- terface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.