Properties of metal–water interfaces studied from first principles

Properties of the metal–water interface have been addressed by periodic density functional theory calculations, in particular with respect to the electronic and geometric structures of water bilayers on several transition metal surfaces. It will be demonstrated that the presence of the metal substrate leads to a significant polarization of the water bilayer. This causes a substantial water-induced reduction of the work function in spite of the weak water–metal interaction, but it is not associated with a significant change of the electronic structure of the metal substrates. The structure and the vibrational spectra of water bilayers at room temperatures have been studied performing ab initio molecular dynamics simulations. The simulations suggest that the water bilayer structure on noble metals is not stable at room temperature, whereas on more strongly interacting metal surfaces some ordering of the water layer persists. In addition, metal–water interfaces under electrochemical conditions, i.e. for charged metal substrates, are addressed. Our simulations show that the charging of the surface leads to characteristic changes in the wall–oxygen distribution and the vibrational spectra. New Journal of Physics 11 (2009) 125003 1367-2630/09/125003+25$30.00 © IOP Publishing Ltd and Deutsche Physikalische Gesellschaft