Reaction mechanism of CO2 on the surface δ-Pu(100):a DFT study

This investigation elucidates the adsorptive and dissociative interactions of CO2 and CO molecules with the δ-Pu (100) 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. [Display omitted] •This manuscript establishes a microscopic model for the adsorption of CO2 gas molecules on the δ-Pu(100) surface, capable of simulating the adsorption and dissociation processes of gas molecules based on first-principles methods.•The research findings demonstrate that CO2 gas molecules exhibit strong adsorption capability on the δ-Pu(100) surface, with an adsorption energy of 9.3654 eV. This is attributed to the significant deformation of CO2 molecules during the adsorption process, showcasing the strong chemical reactivity of the δ-Pu(100) surface.•This manuscript elucidates the microscopic process of the two-step dissociation of CO2 molecules and calculates the dissociation energies separately. The results indicate that the first-step dissociation of CO2 molecules is more likely to occur. This investigation elucidates the adsorptive and dissociative interactions of CO2 and CO molecules with the δ-Pu (100) 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