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 electrification 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 parametrize a cluster expansion of the electrified interface 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.

中文翻译：

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带电固液界面的电压依赖性簇扩展：在过渡金属的电化学沉积中的应用

由于金属-溶液界面的复杂结构以及电极极化过程中表面起电的关键作用，电化学沉积金属单层的详细原子建模具有挑战性。需要包括熵效应以获得准确的表面化学势的进一步挑战了界面电化学平衡的精确模型。我们提出了一种界面环境的嵌入式量子连续谱模型，该模型解决了这些挑战中的每一个，并研究了银在金（100）表面上的欠电势沉积。