title: Insight from first principles into the nature of the bonding between water molecules and 4d metal surfaces.
abstract: We address the nature of the bond between water molecules and metal surfaces through a systematic density-functional theory (DFT) study of H(2)O monomer adsorption on a series of close-packed transition metal surfaces: Ru(0001), Rh(111), Pd(111), and Ag(111). Aiming to understand the origin behind energetic and structural trends along the 4d series we employ a range of analysis tools such as the electron reactivity function, decomposition of densities of states, electron density differences, and inspection of individual Kohn-Sham orbitals. The results obtained from our DFT calculations allow us to rationalize the bonding between water and transition metal surfaces as a balance of covalent and electrostatic interactions. A frontier orbital scheme based on so-called two-center four-electron interactions between the molecular orbitals of H(2)O--mainly the 1b(1)--and d-band states of the surface proves incisive in understanding these systems.
authors.affiliation: Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany.
authors.forename: Javier
authors.initials: J
authors.lastname: Carrasco
authors.forename: Angelos
authors.initials: A
authors.lastname: Michaelides
authors.forename: Matthias
authors.initials: M
authors.lastname: Scheffler