Reaction mechanism of CO2 on the surface δ-Pu(1 0 0):a DFT study

Abstract

This investigation elucidates the adsorptive and dissociative interactions of CO₂ and CO molecules with the δ-Pu (1 0 0) surface, utilizing state-of-the-art first-principles calculations. The study unearths that the hollow site epitomizes the most favorable adsorption locus for both CO₂ and CO. Within the paramount adsorption configuration, there prevails a propensity for both species to partake in dissociative adsorption, characterized by CO₂ cleaving into an O atom and a concomitant CO moiety, whereas CO disintegrates into discrete C and O atoms. The dissociation energy barriers conducive to such configurations are computed to be 3.0568 eV for CO₂ and 5.1667 eV for CO. A thorough analysis of electronic charges and density of states intimates a transfer of electrons from the Plutonium surface atoms to the carbonaceous adsorbates during dissociation. Post dissociation of the C-O bond, the 6d orbitals of Plutonium engage in electronic hybridization with the 2p orbitals of Carbon, culminating in the constitution of ionic bonding.