A molecular dynamics study of the structure of water layers adsorbed on MgO(100)

Molecular dynamics simulations are performed at various temperatures (150-300 K) and coverages (1-3 layers) on the adsorption of water on a clean MgO(100) surface using semiempirical potentials. At the monolayer coverage, a number of very stable (m X n) structures are obtained which differ only by the mutual orientations of the molecules. The p(3 X 2) phase observed above 180 K in low-energy electron diffraction (LEED) and helium atom scattering (HAS) experiments is shown to be the most stable at 200 K and above this temperature. It contains six inequivalenay oriented molecules which lie flat above the cation sites with the hydrogens pointing approximately along the Mg rows. When the water coverage increases, a layer of icelike hexagonal structure within which the water molecules are hydrogen bonded is formed above the stable monolayer. This overlayer, which is stable at 150 K, is not hydrogen bonded to the stable monolayer. At 300 K it tends to break up and to aggregate into a 3D ice structure with strong hydrogen bonding. Examination of the calculated oxygen-oxygen distances d(OO) in the monolayer and in the icelike overlayer, and the comparison with the correlation diagram of the frequency shift and bandwidth of the water infrared spectrum versus d(OO) give a very consistent interpretation of the observed polarized infrared signals. (C) 1998 American Institute of Physics. [S0021-9606(98)70432-5]