摘要: A simple electrostatic treatment of the energetics of sequential solution-phase electron transfers involving metallic clusters and other large solutes is outlined and related to the conventional description for charging of gas-pha... 展开 A simple electrostatic treatment of the energetics of sequential solution-phase electron transfers involving metallic clusters and other large solutes is outlined and related to the conventional description for charging of gas-phase clusters with the objective of linking these phenomena and assessing phenomenologically the role of solvation in the former class of systems. The common occurrence of electron transfer sequencies for solution-phase solutes suggests the concept of 'molecular capacitance', denoting the dependence of the surface charge density upon the electrode potential; the present treatment is related to conventional descriptions of the capacitance of metal electrode-solution interfaces. The notion of the 'potential of zero charge', Epzc, for cluster solutes, which also emerges from the electrostatic treatment, is related to the corresponding quantities for both metal-solution and metal-vacuum interfaces. The analysis therefore provides an instructive link between the charging energetics of spherical clusters and planar surfaces in solution- versus gas-phase environments. 收起