Zooming into the Inner Helmholtz Plane of Pt(111)–Aqueous Solution Interfaces: Chemisorbed Water and Partially Charged Ions

[Image: see text] The double layer on transition metals, i.e., platinum, features chemical metal–solvent interactions and partially charged chemisorbed ions. Chemically adsorbed solvent molecules and ions are situated closer to the metal surface than electrostatically adsorbed ions. This effect is described tersely by the concept of an inner Helmholtz plane (IHP) in classical double layer models. The IHP concept is extended here in three aspects. First, a refined statistical treatment of solvent (water) molecules considers a continuous spectrum of orientational polarizable states, rather than a few representative states, and non-electrostatic, chemical metal–solvent interactions. Second, chemisorbed ions are partially charged, rather than being electroneutral or having integral charges as in the solution bulk, with the coverage determined by a generalized, energetically distributed adsorption isotherm. The surface dipole moment induced by partially charged, chemisorbed ions is considered. Third, considering different locations and properties of chemisorbed ions and solvent molecules, the IHP is divided into two planes, namely, an AIP (adsorbed ion plane) and ASP (adsorbed solvent plane). The model is used to study how the partially charged AIP and polarizable ASP lead to intriguing double-layer capacitance curves that are different from what the conventional Gouy–Chapman–Stern model describes. The model provides an alternative interpretation for recent capacitance data of Pt(111)–aqueous solution interfaces calculated from cyclic voltammetry. This revisit brings forth questions regarding the existence of a pure double-layer region at realistic Pt(111). The implications, limitations, and possible experimental confirmation of the present model are discussed.