Layer-by-layer growth of thin amorphous solid water films on Pt(111) and Pd(111)

The growth of amorphous solid water (ASW) films on Pt(111) is investigated using rare gas (e.g., Kr) physisorption. Temperature programmed desorption of Kr is sensitive to the structure of thin water films and can be used to assess the growth modes of these films. At all temperatures that are experimentally accessible (20-155 K), the first layer of water wets Pt(111). Over a wide temperature range (20-120 K), ASW films wet the substrate and grow approximately layer by layer for at least the first three layers. In contrast to the ASW films, crystalline ice films do not wet the water monolayer on Pt(111). Virtually identical results were obtained for ASW films on epitaxial Pd(111) films grown on Pt(111). The desorption rates of thin ASW and crystalline ice films suggest that the relative free energies of the films are responsible for the different growth modes. However, at low temperatures, surface relaxation or "transient mobility" is primarily responsible for the relative smoothness of the films. A simple model of the surface relaxation semiquantitatively accounts for the observations.