title: Density functional theory studies of UO2(2+) and NpO2(+) complexes with carbamoylmethylphosphine oxide ligands.
abstract: The UO(2)(2+) and NpO(2)(+) extraction complexes with n-octyl(phenyl)-N,N-diisobutylmethylcarbamoyl phosphine oxide (CMPO) and diphenyl-N,N-diisobutylcarbamoyl phosphine oxide (Ph(2)CMPO) have been investigated by density functional theory (DFT) in conjunction with relativistic small-core pseudopotentials. For these extraction complexes, especially the complexes of 2:1 (ligand/metal) stoichiometry, UO(2)(2+) and NpO(2)(+) predominantly coordinate with the phosphoric oxygen atoms. The CMPO and Ph(2)CMPO ligands have higher selectivity for UO(2)(2+) over NpO(2)(+), and for all of the extraction complexes, the metal-ligand interactions are mainly ionic. In most cases, the complexes with CMPO and Ph(2)CMPO ligands have comparable metal-ligand binding energies, that is, the substitution of a phenyl ring for the n-octyl group at the phosphoryl group of CMPO has no obvious influence on the extraction of UO(2)(2+) and NpO(2)(+). Moreover, hydration energies might play an important role in the extractability of CMPO and Ph(2)CMPO for these actinyl ions.
authors.affiliation: Nuclear Energy Nano-Chemistry Group, Key Laboratory of Nuclear Analytical Techniques, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China.
authors.forename: Cong-Zhi
authors.initials: CZ
authors.lastname: Wang
authors.forename: Jian-Hui
authors.initials: JH
authors.lastname: Lan
authors.forename: Yu-Liang
authors.initials: YL
authors.lastname: Zhao
authors.forename: Zhi-Fang
authors.initials: ZF
authors.lastname: Chai
authors.forename: Yue-Zhou
authors.initials: YZ
authors.lastname: Wei
authors.forename: Wei-Qun
authors.initials: WQ
authors.lastname: Shi