Adsorption and dissociation of CO on Fe(110) from first principles

We employ spin-polarized periodic density functional theory (DFT) to characterize CO adsorption and dissociation on the Fe(110) surface. We investigate the site preference for CO on Fe(110) at hCO = 0.25 and 0.5 monolayer (ML), for different functional forms of the generalized gradient approximation (GGA) to electron exchange and correlation within DFT. At 0.25 ML, we predict the existence of a new ordered structure comparable in stability to one proposed previously. At 0.5 ML, we confirm the preference of a distorted on-top adsorption configuration suggested by experiment. The calculated heats of adsorption, CO stretching frequencies, and work function changes agree well with experiment. When dissociating from the on-top site, we predict that CO first moves off the on-top site and then goes through a lying-down transition state with a barrier of 1.52 eV. Diffusion of CO on Fe(110) from the on-top site to the longbridge site is predicted to have a very small barrier of 0.1 eV. Dissociation of CO from the long-bridge site goes through the same transition state as from the on-top site, but the former has a slightly lower barrier. After dissociation, O atoms remain on the surface while C atoms are embedded into Fe(110), indicating C atoms may readily diffuse into Fe(110). 2004 Elsevier B.V. All rights reserved.