It is a general notion in interfacial electrochemistry that the stability of adsorbate phases that only contain hydrogen atoms should be independent of the pH value of the electrolyte on the scale of the reversible hydrogen electrode, whereas the stability of adsorbate phases that do not contain any hydrogen should be independent of the pH value on the scale of the standard hydrogen electrode. In this Perspective, it will be argued on the basis of a grand-canonical approach that such a Nernstian behavior can only be reproduced if the free energy of the adsorbate phase is independent of the electrochemical control parameters. In general, this should not be true, so that the Nernstian behavior should be the exception rather than the rule. Still, structural and chemical factors will be discussed that might lead to a Nernstian behavior. This requires an analysis of the electrochemical electrolyte/electrode interface on the atomistic level. At the same time, this analysis also provides a guideline for the validity of grand-canonical simulations using the concept of the computational hydrogen electrode in which the dependence of the energy of adsorbate phases on pH and electrode potential is neglected.

中文翻译：

---

从理论家的原子观点看界面电化学中的可逆与标准氢电极标度

界面电化学中的一般概念是，仅含有氢原子的吸附相的稳定性应该与可逆氢电极规模上的电解质 pH 值无关，而不含任何氢的吸附相的稳定性应与标准氢电极刻度上的 pH 值无关。在这个观点中，将基于大规范方法论证这种能斯特行为只有在吸附相的自由能独立于电化学控制参数的情况下才能重现。一般来说，这不应该是真的，因此 Nernstian 的行为应该是例外而不是规则。尽管如此，仍将讨论可能导致 Nernstian 行为的结构和化学因素。这需要在原子水平上分析电化学电解质/电极界面。同时，该分析还为使用计算氢电极概念的大规范模拟的有效性提供了指导，其中忽略了吸附物相的能量对 pH 和电极电位的依赖性。