Relativistic density functional theory modeling of plutonium and americium higher oxide molecules

Zaitsevskii, Andréi; Mosyagin, N. S.; Титов, А. В.; Kiselev, Yuri M.

doi:10.1063/1.4813284

Cited by 19 publications

(49 citation statements)

References 25 publications

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“…Concerning the oxygen ligands, PuO 4 was predicted to be D 4h , 3 a result verified by ref 11. There are experimental claims based on thermochromatography 26 and on ozonization of Pu(VI) alkaline solutions, 27 combined with radioactivity transfer or optical spectra.…”

Section: Introductionmentioning

confidence: 81%

Is Octavalent Pu(VIII) Possible? Mapping the Plutonium Oxyfluoride Series PuO_nF_8–2n (n = 0–4)

Huang

Pyykkö²,

2015

Inorg. Chem.

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While the oxidation state Pu(VIII) is shown to be less stable than Pu(V) in the PuO4 molecule, it is not clear if the more electronegative fluorine can help to stabilize Pu(VIII). Our calculations on PuO(n)F(8-2n) (n = 0-4) molecules notably confirm that PuO2F4 has both (1)D(4h) and (5)C(2v) minima with the oxidation states Pu(VIII) and Pu(V), respectively, with the latter having lower energy. The hybrid-DFT, CCSD(T), and CASSCF methods all give the same result. The results conform to a superoxide ligand when n ≥ 2. PuF8 in a (1)O(h) state can decompose to PuF6 and F2, and PuOF6 in a (1)C(2v) state also can break down to PuF6 and 1/2 O2. The Pu(VIII) anion PuO2F5(-) does have a D(5h) minimum, which also lies above a (5)C(2v) Pu(V) peroxide structure. However, the energy differences between the different minima are not large, indicating that metastable species with oxidation states higher than Pu(V) cannot be completely excluded.

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Section: Introductionmentioning

confidence: 81%

Is Octavalent Pu(VIII) Possible? Mapping the Plutonium Oxyfluoride Series PuO_nF_8–2n (n = 0–4)

Huang

Pyykkö²,

2015

Inorg. Chem.

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“…The molecular subvalence / valence many-electron problem was solved by the non-collinear 2c RDFT technique with the fully unrestricted optimization of Kohn-Sham one-electron spinors using the code described in Ref. The hybrid PBE0 approximation 25 for the exchangecorrelation functional was chosen both because of its (partially) non-empirical nature and its successful use in previous electronic structure calculations on actinide compounds 5,13 . The components of the spinors were expanded in a basis comprising contracted Gaussian set [8s8p6d5f2g] centered on the actinide atom 24 and [6s4p2d] sets on the oxygen atoms (cf.…”

Section: Methodsmentioning

confidence: 99%

“…The possibility of reaching high oxidation states of plutonium and early transplutonium elements in their gas-phase oxides has been discussed during several decades (see e. g. [1][2][3][4][5][6]. To date, it seems clear that the formation of thermodynamically stable simple molecular oxides (VII) and (VIII) is not excluded for Pu, hardly probable for Am and improbable for Cm 5,7,8 ; the oxidation state of Cm in hypothetical metastable CmO 4 apparently should be identified as (VI).…”

Section: Introductionmentioning

confidence: 99%

Plutonium and transplutonium element trioxides: molecular structures, chemical bonding, and isomers

Zaitsevskii

2015

Phys. Chem. Chem. Phys.

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Ground-state equilibrium geometries, energetics, and vibrational frequencies of AnO3 molecules, An = Pu through Cf, and their isomers are calculated using an accurate small-core pseudopotential model and the two-component relativistic density functional theory. The qualitative features of chemical bonding in these molecules are discussed in terms of oxidation states and bond orders. The actinide oxidation state (VI) is reached only in the plutonium trioxide molecule, whereas heavier actinide atoms in T-shaped trioxide molecules should be considered as pentavalent. At least at low temperatures, PuO3 and, to a lesser degree, AmO3 and BkO3 molecules should be stable both with respect to the isomerization into oxoperoxides or oxosuperoxides and the decay into dioxides and molecular oxygen. These trioxides can form dimers with significant (above 250 kJ mol(-1)) dissociation energies; the oxidation states of actinide atoms in the lowest-energy configurations of these dimers coincide with those in the corresponding monomers. The ability to reach high oxidation states in oxygen compounds gradually decreases from Pu onwards, with the only exception being the unexpectedly stable Bk(v)O3.

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“…The noncollinear 2c RDFT computational scheme within the valence GRECP approximation was applied to electronic structure modeling of higher oxide molecules of plutonium and early transplutonium elements . These systems are of interest from the point of view of general chemistry and theory of chemical structure (due to the possibility of reaching extremely high oxidation states) and because of the problem of identification of volatile compounds of these actinides presumably formed in oxidative media (see Refs.…”

Section: Molecular Calculationsmentioning

confidence: 99%

Generalized relativistic effective core potentials for actinides

Mosyagin

Zaitsevskii

Skripnikov

et al. 2015

Int J of Quantum Chemistry

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Actinide compounds are very intriguing objects for the quantum chemistry because, on the one hand, these compounds are of great scientific and technological interest and, on the other hand, quantitative first principle based modeling of their electronic structure is extremely difficult because of strong relativistic effects and complicated electron correlation pattern. The efficiency of high-level all-electron relativistic methods in applications to complex actinide systems of practical interest is questionable and more economical but sufficiently accurate approaches to the studies of such systems are preferable. Recently, generalized relativistic effective core potentials (GRECPs) have been generated for actinides to perform accurate calculations of electronic structure and properties of their compounds with moderate computational cost. The accuracy of different GRECP versions is analyzed in atomic calculations and their applications to molecular and cluster calculations are reviewed. The results are compared with available experimental data and other theoretical studies.

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Relativistic density functional theory modeling of plutonium and americium higher oxide molecules

Cited by 19 publications

References 25 publications

Is Octavalent Pu(VIII) Possible? Mapping the Plutonium Oxyfluoride Series PuO_nF_8–2n (n = 0–4)

Is Octavalent Pu(VIII) Possible? Mapping the Plutonium Oxyfluoride Series PuO_nF_8–2n (n = 0–4)

Plutonium and transplutonium element trioxides: molecular structures, chemical bonding, and isomers

Generalized relativistic effective core potentials for actinides

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Relativistic density functional theory modeling of plutonium and americium higher oxide molecules

Cited by 19 publications

References 25 publications

Is Octavalent Pu(VIII) Possible? Mapping the Plutonium Oxyfluoride Series PuOnF8–2n (n = 0–4)

Is Octavalent Pu(VIII) Possible? Mapping the Plutonium Oxyfluoride Series PuOnF8–2n (n = 0–4)

Plutonium and transplutonium element trioxides: molecular structures, chemical bonding, and isomers

Generalized relativistic effective core potentials for actinides

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Product

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Is Octavalent Pu(VIII) Possible? Mapping the Plutonium Oxyfluoride Series PuO_nF_8–2n (n = 0–4)

Is Octavalent Pu(VIII) Possible? Mapping the Plutonium Oxyfluoride Series PuO_nF_8–2n (n = 0–4)