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Separation of trivalent actinide (An(III)) and lanthanide (Ln(III)) is a worldwide challenge of nuclear waste treatment. Designing ligands with efficient An(III)/Ln(III) separation performance is still one of the key issues for the disposal of accumulated radioactive waste and the recovery of minor actinides. Recently, N-heterocyclic ligands modified with amide groups have shown excellent An(III)/Ln(III) separation performance. The preorganized structure of the ligands has a great impact on the An(III)/Ln(III) separation performance. We theoretically investigated the extraction behaviors of Am(III) and Eu(III) using phenanthroline (L1 and L2) and bipyridine (L3 and L4) based ligands with a completely or partially preorganized structure. The properties of these ligands and their coordination structures, bonding nature and thermodynamic behaviors with the Am(III) and Eu(III) complexes have been systematically studied in a theoretical fashion. The analyses of the bonding nature suggest that the Am-N bonds possess more covalence than the Eu-N bonds. The thermodynamic results indicate that L2 with a completely preorganized structure has the strongest extraction ability and the best Am(III)/Eu(III) selectivity, while L3 with the most flexible skeleton appears to have the weakest extraction ability and the lowest Am(III)/Eu(III) selectivity. And L1 and L4 have similar performances with regard to Am(III)/Eu(III) selectivity. The results suggest that a certain degree of preorganization of the ligand structure can enhance the extraction ability and Am(III)/Eu(III) selectivity. This work provides valuable information for designing efficient ligands for An(III)/Ln(III) separation by the preorganization strategy.

Efficient separation of neptunium and plutonium from spent nuclear fuel is essential for advanced nuclear fuel cycles. At present, the development of effective actinide separation ligands has become a top priority. As common adsorbents for extracting uranium from seawater, amidoxime-based adsorbents may also be able to separate actinides from high-level liquid waste (HLLW). In this work, the complexation of Np(IV,V,VI) and Pu(IV) and alkyl chains (R = C13H26) modified with amidoximate (AO−) and carboxyl (Ac−) functional groups was systematically studied by quantum chemical calculations. For all the studied complexing species, the RAc− and RAO− ligands act as monodentate or bidentate ligands. Complexes with AO− groups show higher covalency of the metal–ligand bonding than the analogues with Ac− groups, in line with the binding energy analysis. Bonding analysis verifies that these amidoxime/carboxyl-based adsorbents possess higher coordination affinity toward Pu(IV) than toward Np(IV), and the Np(VI) complexes have stronger covalent interactions than Np(V). According to thermodynamic analysis, these adsorbents have the ability to separate Np(IV,V,VI) and Pu(IV), and also exhibit potential performance for partitioning Pu(IV) from Np(IV) under acidic conditions. This work can help to deeply understand the interaction between transuranium elements and amidoxime-based adsorbents, and provide a theoretical basis for the separation of actinides with amidoxime-based adsorbents.

Mutual separation of trivalent americium (Am3+) and curium (Cm3+) ions through liquid-liquid extraction is challenging due to the similarity in their chemical properties. Three N, O combined extractants 2,6-pyridinedicarboxylic acid di(N-ethyl-4-fluoroanilide) (Et(pFPh)DPA), diphenyl(2-pyridyl)phosphine oxide (Ph2PyPO), and alkyldiamide amine with 2-ethylhexylalkyl chains (ADAAM(EH)) have been identified to exhibit selectivity for Am3+ over Cm3+. In this work, the structures, bonding nature, and thermodynamic behaviors of a series of representative Am- and Cm-complexes with these ligands have been systematically investigated using density functional theory (DFT) calculations. Based on our calculations, the ONO angle formed by three donor atoms of the ligand in the Am-complex is slightly larger than that in its Cm-analogue. The studied ligands show their preference toward Am3+ by opening their "mouths" slightly wider. According to the Mayer bond order and the quantum theory of atoms in molecules (QTAIM) analyses, the interactions between the O donor atoms of these ligands and Am3+ and Cm3+ ions show some weak partial covalent character, and compared to the Am-O bond, there is relatively more covalency in the Cm-O bond in the corresponding complex. However, opposite results can be found in the Am-N and Cm-N bonding for the first two ligands. Particularly, for the better separation ligand ADAAM(EH), the Am-N and Cm-N interactions are extremely weak and no covalent character exists in the bonding. Nevertheless, the difference between the very weak Am-N and Cm-N interactions still leads to a better performance of ADAAM(EH). Based on the comparison of these ligands, we can find that weakening the binding ability of N atoms in the ligand may increase the difference between the Am-N and Cm-N interactions, thus enhancing the Am3+/Cm3+ separation ability of the ligand. Our study might provide new insights into understanding the selectivity of these three N, O combined ligands toward minor actinides and pave the way for designing efficient Am3+/Cm3+ extraction and separation ligands.

To evaluate how halogen and actinide atoms affect the electronic structures and bonding nature, we have theoretically investigated a series of the actinide halides An(TRENTIPS)X (An = Th-Pu; X = F-I); several of them have been synthesized by Liddle's group. The An-X bond distances decrease from An = Th to Pu for the same halides, and the harmonic vibrational frequencies for the An-X bonds are more susceptible to being affected by the halogen atoms. The analyses of bonding nature reveal that the An-X bonds have a certain covalency with a polarized character, and the σ-bonding component in the total orbital contribution is greatly larger than the corresponding π-bonding ones based on the analysis of the NOCVs (the natural orbitals for chemical valence). Furthermore, the electronic structures of the thorium complexes are obviously different from those of the uranium and transuranic analogues due to more valence electrons in Th 6d orbitals. In addition, thermodynamic results suggest that the U(TRENTIPS)Br complex is the most stable and U(TRENTIPS)Cl has the highest reactivity based on the halide exchange reaction of U(TRENTIPS)X complexes using Me3SiX. The reduction ability of the tetravalent An(TRENTIPS)X is sensitive to halogen atoms according to the calculated electron affinity of the An(TRENTIPS)X and the reactions An(TRENTIPS)X + K → An(TRENTIPS) + KX. This work presents the effect of the halogen and the actinide atoms on the structures, bonding nature and redox ability of a series of the tetravalent actinide halides with TREN ligand and facilitates our in-depth understanding of f-block elements, which could provide theoretical guidance for experimental work on actinide halides, especially for the synthetic chemistry of transuranic halides.

Phenanthroline based ligands have shown potential performance for partitioning trivalent actinides from lanthanides. In this work, we have explored four ester and amide ligands based on the phenanthroline skeleton and elucidated the separation mechanism between Am(iii) and Eu(iii) ions. The molecular geometries and extraction reactions of the metal-ligand complexes were modeled by using scalar-relativistic density functional theory. The results show that the amide based ligands have stronger coordination ability with the metal ions than the corresponding ester based ligands. According to the thermodynamic results, ligands N,N'-diethyl-N,N'-ditolyl-2,9-diamide-1,10-phenanthroline (L2) and N,N'-(1,10-phenanthroline-2,9-diyl)bis(N-ethyl-P-methyl-N-(p-tolyl)phosphinic amide) (L4) appear to have the strongest complexing ability, which is supported by the result of electrostatic potential (ESP) and the M-OL bond orders. Moreover, ligand L2 has excellent selectivity for Am(iii)/Eu(iii) among the four ligands. Additionally, the bonding properties between the metal ions and the ligands reveal that the Am(iii)/Eu(iii) selectivity stems from the Am-N bonds with more covalent character, which is supported by the analysis of the hardness of the ligands and the bond orders. This work provides useful information for understanding the Am(iii)/Eu(iii) selectivity of phenanthroline derived ligands bearing ester and amide groups.

In recent years, there has been a trend to use synergistic systems of neutral and acidic extractants into a single-solvent formulation to achieve Ln3+/An3+ extraction and separation via simplified processing schemes. In this study, geometrical structures, bonding nature, and thermodynamic stabilities of a series of possible extraction complexes of Am3+ and Eu3+ with two neutral-acid synergistic systems (CMPO-HDEHP and CMPO-HEH[EHP]) were theoretically studied using scalar-relativistic density functional theory (DFT). It is found that hydrogen bonds between neutral and acid ligands may greatly influence the Eu3+/Am3+ extraction and separation performance of the two synergistic systems. According to natural bond orbital (NBO) and energy decomposition analyses (EDA), the phosphoryl oxygen atoms of HDEHP or HEH[EHP] have higher affinity for Eu3+ and Am3+ than those of the CMPO ligand. Since weak but different extents of covalency exist in Eu- and Am-complexes, Eu3+/Am3+ separation via these two systems may be attributed to the different compositions of interactions between the metal ions and ligands. Thermodynamic analysis shows that the neutral complexes ML(NO3)2 (M = Eu and Am; L = [CMPO-DEHP]- and [CMPO-EH[EHP]]-) appear to be the most probable species in the complexation process.

Synthesis of complexes with direct actinide–actinide (An–An) bonding is an experimental ‘holy grail’ in actinide chemistry. In this work, a series of actinide dimetallocenes An2Cp*2 (Cp* = C5(CH3)5, An = Th–Pu) with An–An multiple bonds have been systematically investigated using quantum chemical calculations. The coaxial Cp*–An–An–Cp* structures are found to be the most stable species for all the dimetallocenes. A Th–Th triple bond is predicted in the Th2Cp*2 complex, and the calculated An–An bond orders decrease across the actinide series from Pa to Pu. The covalent character of the An–An bonds is analyzed by using natural bond orbitals (NBO), molecular orbitals (MO), the quantum theory of atoms in molecules (QTAIM), and electron density difference (EDD). While Th 6d orbitals dominate the Th–Th bonds in Th2Cp*2, the An 6d-orbital characters decrease and 5f-orbital characters increase for complexes from Pa2Cp*2 to Pu2Cp*2. All these actinide dimetallocenes are stable in the gas phase relative to the AnCp* reference at room temperature. Based on the reactions of AnCp*2 and An, Th2Cp*2, Pa2Cp*2 and possibly also U2Cp*2 should be accessible as isolated molecules under suitable synthetic conditions. Our results shed light on the molecular design of ligands for stabilizing actinide–actinide multiple bonds.

Due to the similar chemical properties of actinides An(iii) and lanthanides Ln(iii), their separation in spent nuclear fuel reprocessing is extremely challenging. A 1,10-phenanthroline dipicolinamide-based ligand (PhenBHPPA) has been identified to possess a selectivity for Am(iii) over Eu(iii) and could potentially be used for group actinide extraction. In this study, quasi-relativistic density functional theoretical calculations have been used to disclose the interaction mechanisms of Am(iii) and Eu(iii) complexes with PhenBHPPA. The electronic structures, bonding nature, QTAIM (Quantum Theory of Atoms in Molecules) analyses and thermodynamic behaviors of the Am(iii) and Eu(iii) complexes with PhenBHPPA have been explored in detail. According to the Wiberg bond indices (WBIs) and QTAIM analyses, interactions between the ligand and metal cations (Am(iii) and Eu(iii)) exhibit a weakly covalent character. Thermodynamic analyses show that the charged complexes [ML(NO3)2](+) appear to be the most stable species in the complexation processes. Moreover, it is more energetically favorable for PhenBHPPA to bind to Am(iii) compared to Eu(iii). Our study could render new insights into understanding the selectivity of the ligand towards minor actinides and the separation of An(iii) from Ln(iii) via liquid-liquid extraction.

Actinide separation in spent nuclear fuel reprocessing is essential for the closed nuclear fuel cycle. Organophosphorus reagents have been found to exhibit strong affinities for actinides in experiments. In this work, the extraction complexes of AnO2(n+) (An = U, Np; n = 1, 2) with the traditional organophosphorus ligand HDEHP (di-(2-ethylhexyl)phosphoric acid) have been investigated using density functional theory together with scalar-relativistic effective core potentials (ECPs) for actinide elements. According to our calculations, the HDEHP dimer prefers to act as a bidentate ligand in most of the studied complexes. HDEHP ligands show a higher extraction ability for An(vi) over An(v), and the formation of Np(vi) complexes is slightly more favorable than those of U(vi) analogues, which is mainly attributed to the stronger donor-acceptor interaction in Np(vi) complexes. The intramolecular hydrogen bonds play a significant role in the stability of the 1 : 1 type complexes AnO2(HL)2(NO3)2 (L = DEHP(-)). Moreover, AnO2(HL)2(NO3)2 are the most stable species in nitrate-rich acid solutions, while at low nitric acid concentrations, the complexing reaction of AnO2(H2O)5(2+) + 2(HL)2 → AnO2(HL2)2 + 2H(+) + 5H2O is probably the dominant reaction in the extraction process. Our results can help to understand the speciation of actinyl complexes in real solvent extraction of actinides with HDEHP at the molecular level.