Prediction of the structures and heats of formation of MO2, MO3, and M2O5 for M = V, Nb, Ta, Pa

Lontchi, Eddy M.; Mason, Marcos M.; Vasiliu, Monica; Dixon, David A.

doi:10.1039/d3cp00380a

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“…There are two higher energy isomeric structures C 2 v and C 3 v . In a study comparing the Pa 2 O 5 dimer with the transition metal M 2 O 5 (M = V, Nb, and Ta) dimers, we predicted the formation of three oxygen-bridged isomers, mono-, di-, and tribridge . The tribridge Pa 2 O 5 isomer was predicted to be the lowest energy isomer, with the dibridge and monobridge higher in energy by 12.7 and 34.2 kcal/mol, respectively.…”

Section: Resultsmentioning

confidence: 96%

“…39 In a study comparing the Pa 2 O 5 dimer with the transition metal M 2 O 5 (M = V, Nb, and Ta) dimers, we predicted the formation of three oxygenbridged isomers, mono-, di-, and tribridge. 40 The tribridge Pa 2 O 5 isomer was predicted to be the lowest energy isomer, with the dibridge and monobridge higher in energy by 12 1. The energetics for the reaction at the DFT/B3LYP results are reported in the Supporting Information.…”

Section: ■ Resultsmentioning

confidence: 99%

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Hydrolysis Reactions of the High Oxidation State Dimers Th₂O₄, Pa₂O₅, U₂O₆, and Np₂O₆. A Computational Study

Lontchi,

Vasiliu,

Dixon

2023

J. Phys. Chem. A

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The energetics of the hydrolysis reactions for high oxidation states of the dimeric actinide species Th2 IVO4, Pa2 VO5, and U2 VIO6 were calculated at the CCSD(T) level and those for triplet Np2 VIO6 at the B3LYP level. Hydrolysis is initiated by the formation of a Lewis acid/base adduct with H2O (physisorbed product), followed by a proton transfer to form a dihydroxide molecule (chemisorbed product); this process was repeated until the initial actinide oxide is fully hydrolyzed. For Th2O4, hydrolysis (chemisorption) by the initial and subsequent H2O molecules prefers proton transfer to terminal oxo groups before the bridge oxo groups. The overall Th2O4 hydration pathway is exothermic with chemisorbed products preferred over the physisorption products, and the fully hydrolyzed Th2(OH)8 can form exothermically. Hydrolysis of Pa2O5 forms isomers of similar energies with no initial preference for bridge or terminal hydroxy groups. The most exothermic hydrolysis product for Pa is Pa2O(OH)8 and the most stable species is Pa2O(OH)8(H2O). Hydrolysis of U2O6 and Np2O6 with strong [OAnO]2+ actinyl groups occurs first at the bridging oxygens rather than at the terminal oxo groups. The U2O6 and Np2O6 pathways predict hydrated products to be more favored than hydrolyzed products, as more H2O molecules are added. The stability of the U and Np clusters is predicted to decrease with increasing number of hydroxyl groups. The most stable species on the hydration reaction coordinate for U and Np is An2O3(OH)6(H2O).

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Section: Resultsmentioning

confidence: 96%

Section: ■ Resultsmentioning

confidence: 99%

Hydrolysis Reactions of the High Oxidation State Dimers Th₂O₄, Pa₂O₅, U₂O₆, and Np₂O₆. A Computational Study

Lontchi,

Vasiliu,

Dixon

2023

J. Phys. Chem. A

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Prediction of the structures and heats of formation of MO₂, MO₃, and M₂O₅ for M = V, Nb, Ta, Pa

Abstract: Mono-, di-, and tri-bridge isomers of M2O5 as well as those for the MO2 and MO3 fragments for M = V, Nb, Ta, and Pa were optimized at the density...

Cited by 1 publication

References 111 publications

Hydrolysis Reactions of the High Oxidation State Dimers Th₂O₄, Pa₂O₅, U₂O₆, and Np₂O₆. A Computational Study

Hydrolysis Reactions of the High Oxidation State Dimers Th₂O₄, Pa₂O₅, U₂O₆, and Np₂O₆. A Computational Study

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Prediction of the structures and heats of formation of MO2, MO3, and M2O5 for M = V, Nb, Ta, Pa

Abstract: Mono-, di-, and tri-bridge isomers of M2O5 as well as those for the MO2 and MO3 fragments for M = V, Nb, Ta, and Pa were optimized at the density...

Cited by 1 publication

References 111 publications

Hydrolysis Reactions of the High Oxidation State Dimers Th2O4, Pa2O5, U2O6, and Np2O6. A Computational Study

Hydrolysis Reactions of the High Oxidation State Dimers Th2O4, Pa2O5, U2O6, and Np2O6. A Computational Study

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Prediction of the structures and heats of formation of MO₂, MO₃, and M₂O₅ for M = V, Nb, Ta, Pa

Hydrolysis Reactions of the High Oxidation State Dimers Th₂O₄, Pa₂O₅, U₂O₆, and Np₂O₆. A Computational Study

Hydrolysis Reactions of the High Oxidation State Dimers Th₂O₄, Pa₂O₅, U₂O₆, and Np₂O₆. A Computational Study