Computational treatment of the interaction of carbon monoxide with extended surfaces

Abstract

The interaction of carbon monoxide with extended surfaces of transition metals is treated computationally. The heat of adsorption is composed largely of a CO acceptor contribution, and the surface metal atoms are rehybridized by chemisorption of CO. This leads to a decrease in surface $d$ population and a decrease in $p$,$d$ dipole moment perpendicular to the surface. Both effects are manifested in surface core shifts and work-function changes which have been reported. The impurity-CO interaction is a local effect in which covalent interactions control the attractive or repulsive nature of the interaction. An increase in CO $2{\pi }^{*}$ molecular-orbital population is induced by interaction with alkali-metal atoms.