First principles calculation is performed to study the co-adsorption behaviors of O_(2)and CO_(2)onδ-Pu(100)surface by using a slab model within the framework of density functional theory(DFT).The results demonstrate...First principles calculation is performed to study the co-adsorption behaviors of O_(2)and CO_(2)onδ-Pu(100)surface by using a slab model within the framework of density functional theory(DFT).The results demonstrate that the most favorable co-adsorption configurations are T_(v)-C_(4)O_(7)and T_(p1)-C_(2)O_(8),with adsorption energy of-17.296 e V and-23.131 e V for CO_(2)-based and O_(2)-based system,respectively.The C and O atoms mainly interact with the Pu surface atoms.Furthermore,the chemical bonding between C/O and Pu atom is mainly of ionic state,and the reaction mechanism is that C 2 s,C 2 p,O 2s,and O 2p orbitals overlap and hybridize with Pu 6 p,Pu 6 d,and Pu 5 f orbital,resulting in the occurrence of new band structure.The adsorption and dissociation of CO_(2)molecule are obviously promoted by preferentially occupying adsorbed O atoms,therefore,a potential CO_(2)protection mechanism for plutonium-based materials is that in CO_(2)molecule there occurs complete dissociation of CO_(2)→C+O+O,then the dissociated C atom combines with O atom from O_(2)dissociation and produces CO,which will inhibit the O_(2)from further oxidizing Pu surface,and slow down the corrosion rate of plutoniumbased materials.展开更多
文摘First principles calculation is performed to study the co-adsorption behaviors of O_(2)and CO_(2)onδ-Pu(100)surface by using a slab model within the framework of density functional theory(DFT).The results demonstrate that the most favorable co-adsorption configurations are T_(v)-C_(4)O_(7)and T_(p1)-C_(2)O_(8),with adsorption energy of-17.296 e V and-23.131 e V for CO_(2)-based and O_(2)-based system,respectively.The C and O atoms mainly interact with the Pu surface atoms.Furthermore,the chemical bonding between C/O and Pu atom is mainly of ionic state,and the reaction mechanism is that C 2 s,C 2 p,O 2s,and O 2p orbitals overlap and hybridize with Pu 6 p,Pu 6 d,and Pu 5 f orbital,resulting in the occurrence of new band structure.The adsorption and dissociation of CO_(2)molecule are obviously promoted by preferentially occupying adsorbed O atoms,therefore,a potential CO_(2)protection mechanism for plutonium-based materials is that in CO_(2)molecule there occurs complete dissociation of CO_(2)→C+O+O,then the dissociated C atom combines with O atom from O_(2)dissociation and produces CO,which will inhibit the O_(2)from further oxidizing Pu surface,and slow down the corrosion rate of plutoniumbased materials.
