Interfacial water: A first principles molecular dynamics study of a nanoscale water film on salt

Density functional theory (DFT) molecular dynamics simulations of a thin (∼15 Å) water film on NaCl(001) have been performed, with the aim of understanding the structural and dynamic properties of this important interfacial water system. The interaction of the water film with the surface orders the water molecules in the immediate vicinity of the interface. This is reflected by oscillations in the planar-averaged water density distribution along the surface normal that extend to about 8 Å from the surface. The interaction with the substrate leaves many of the water molecules in the immediate vicinity with broken hydrogen bonds and as a consequence considerably reduced dipole moments. Indeed a clear correlation between the number of hydrogen bonds which a water molecule is involved in and its dipole moment for both water on NaCl and bulk water is observed. How the DFT results obtained here compare to those obtained with various empirical potentials is briefly discussed.