| Abstract
| - The structure and bonding of halogens on various transition metal low-index surfaces has been studied bymeans of density functional theory (DFT) calculations using periodic slabs to model the surface. This approachis shown to be capable of reproducing available experimental data of naked and halogen-covered surfaces.Periodic trends are discerned and discussed for several properties, including metal−halogen bond distancesand vibrational frequencies, adsorption energies, and bond ionicities, which have been evaluated by a Baderpopulation analysis of the corresponding density. A simple correlation is discerned, relating the bond ionicityto the metal work function, so that higher work function surfaces are associated with more covalent bonding.Periodic trends in bond ionicities and metal−halogen vibrational frequencies are in harmony with correspondingdata derived in an electrochemical environment, indicating that the metal−halogen bonding in vacuum sharesome features with the electrode metal surface−halogen bonding.
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