Strain relief and disorder in commensurate water layers formed on Pd(111)

Abstract

Water adsorbs and desorbs intact on Pd(111), forming a hydrogen-bonded wetting layer whose structure we examine by low energy electron diffraction (LEED) and He atom scattering (HAS). LEED shows that water forms commensurate (√3 × √3)R30° clusters that aggregate into a partially ordered, approximately (7 × 7) superstructure as the layer completes. HAS indicates that the water layer remains disordered on a local (approximately 10 Å) scale. Based on workfunction measurements and density functional theory simulations we propose that water forms small, flat domains of a commensurate (√3 × √3)R30° water network, separated by disordered domain boundaries containing largely H-down water. This arrangement allows the water layer to adapt its density and relieve the lateral strain associated with adsorbing water in the optimum flat atop adsorption site. We discuss different possibilities for the structure of these domain walls and compare this strain relief mechanism to the highly ordered, large unit cell structures formed on surfaces such as Pt(111).