Systematic analysis of structural and topological properties: new insights into PuO2(H2O)n2+(n = 1–6) complexes in the gas phase

Li, Peng; Niu, Wenxia; Gao, Tao

doi:10.1039/c6ra27087e

Cited by 10 publications

(9 citation statements)

References 54 publications

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“…The two pathways both happen along the triplet spin surface. It is worth noting that, as you can see, the reaction mechanism of Pu+N2 is similar to that of Pu+O2 [11] and Pu+H2O [13] , plutonium atoms interact with gas molecules to dissociate them, and the atoms after dissociation form bonds with plutonium atoms.…”

Section: Fig2 the Relative Energies Of All Intermediates And Transition States Involved In The Two Reaction Pathways Compositesmentioning

confidence: 85%

“…Therefore, it is necessary to study the reaction mechanism of corrosion process from microscopic point of view. In recent years, there are scholars have done quantum chemical calculations on the detailed reaction mechanism of gas actinides atoms and gas small molecules, including Pu+O2 [11], U + (U 2+ )+H2O [12], Pu+H2O [13], etc. They obtained multiple reaction pathways of these reactions and the geometric structures of each stationary point along the reaction pathway.…”

Section: Introductionmentioning

confidence: 99%

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Quantum chemical study of reaction mechanism between plutonium and nitrogen

et al. 2021

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The study of the reaction between plutonium and nitrogen is helpful to further understand the interaction between plutonium and air gas molecules. For the nitridation reaction of plutonium, there is no report on the microscopic reaction mechanism of this system at present. Therefore, the microcospic mechanism of gas phase reaction of Pu with N2 is studied in this paper based on the density functional theory (DFT) using different functions. In this paper, the geometry of stationary points on the potential energy surface is optimized. In addition, the transition states are verified by the frequency analysis method and the intrinsic reaction coordinate (IRC) method. Finally, we obtain the reaction potential energy curve and the micro reaction pathways. The analysis of reaction mechanism shows that the reaction of Pu with N2 has two pathways. The pathway-1 (Pu+N2→R1→TS1→PuN2) has a T-shaped transition state and the pathway-2 (Pu+N2→R2→TS2→PuN+N) has a L-shaped transition state. Moreover, both transition states have only one virtual frequency. The energy analysis shows that pathway-1 is the main reaction pathway. The nature of the Pu-N bonding evolution along the pathways is studied by atoms in molecules (AIM) and electron localization function (ELF) topological approaches. In order to analyse the role of 5f orbital of plutonium atom in the reaction, the variation of density of state along the pathways is performed. The results show that the 5f orbital makes major contributions to the formation of Pu-N bonds. Meanwhile, the influence of different temperatures on the reaction rate is revealed by calculating the rate constants of the two reaction pathways.

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Section: Fig2 the Relative Energies Of All Intermediates And Transition States Involved In The Two Reaction Pathways Compositesmentioning

confidence: 85%

Section: Introductionmentioning

confidence: 99%

Quantum chemical study of reaction mechanism between plutonium and nitrogen

et al. 2021

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“…This is consistent with the more negative natural population analysis (NPA) charge on O carbonyl than on N amine that results from the more charge transfer from ligand to metal upon formation of M(HMNTA) 2 4+ . QTAIM analysis at the BCPs are summarized in Table . , Notably, the QTAIM method is a successful strategy to analyze the bonding features in metal complexes. , As for the M(HMNTA) 2 4+ complexes, the small ρ(r), positive ∇ 2 ρ(r) and negative H(r) with small magnitude indicate the presence of dative M–O carbonyl bonds . Although there seems to be dative interactions between M 4+ and N amine according to the QTAIM parameters, most of the values are much smaller than those at the M–O carbonyl BCPs.…”

Section: Resultsmentioning

confidence: 99%

HMNTA Complexes of Tetravalent Metal Ions: On the Roles of Carbonyl Oxygen and Amine Nitrogen in the Stabilization of Gas-Phase M(HMNTA)₂⁴⁺Complexes

Chen

Xiong

Gong

2021

J. Am. Soc. Mass Spectrom.

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Gas-phase tetrapositively charged M(HMNTA) 2 4+ (M = Zr, Hf, Th, and U) ions were generated via electrospray ionization of the M(ClO 4 ) 4 and N,N,N′,N′,N″,N″-hexamethylnitrilotriacetamide (HMNTA) mixtures in acetonitrile. In these complexes, the Zr 4+ , Hf 4+ , Th 4+ , and U 4+ metal centers are coordinated by two neutral HMNTA ligands forming antitriangular prism geometry on the basis of DFT calculations. Bonding analysis reveals that the M 4+ center is stabilized by six carbonyl oxygen atoms, while the interactions between M 4+ and two central amine nitrogen atoms are negligible. This is further confirmed by the calculation results of two tetrapositive model complexes without either central amine nitrogen or carbonyl oxygen atoms, indicating the central nitrogen atom of HMNTA is not necessary in forming tetrapositive metal complexes that can be stabilized in gas phase. Collision-induced dissociation of Zr(HMNTA) 2 4+ , Hf(HMNTA) 2 4+ , and Th(HMNTA) 2 4+ shows the formation of similar charge reducing products with the oxidation state of metal retaining IV whereas ions with other oxidation states were observed for the fragmentation products of U(HMNTA) 2 4+ .

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“…It is worth emphasizing that ELF + AIM analysis are powerful tools to analyzing the nature of the interaction between atoms, and have been successfully used in the actinide system. [47][48][49][50][51][52][53] The ELF shaded surfaces with projection maps of stationary points on the PuO + H 2 O potential energy surface optimized at the PW91/SDD levels of theory are displayed in Fig. 5.…”

Section: Bonding Characteristicsmentioning

confidence: 99%

Can water continuously oxidize the PuO molecule? Mechanisms, topological analysis and rate constant calculations

Niu

Xie

et al. 2018

RSC Adv.

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Systematic analysis of structural and topological properties: new insights into PuO₂(H₂O)_n²⁺(n = 1–6) complexes in the gas phase

Abstract: In this study, the equilibrium, electronic structures, bonding and topological properties of PuO2(H2O)n2+ (n = 1–6) complexes were systematically investigated.

Cited by 10 publications

References 54 publications

Quantum chemical study of reaction mechanism between plutonium and nitrogen

Quantum chemical study of reaction mechanism between plutonium and nitrogen

HMNTA Complexes of Tetravalent Metal Ions: On the Roles of Carbonyl Oxygen and Amine Nitrogen in the Stabilization of Gas-Phase M(HMNTA)₂⁴⁺Complexes

Can water continuously oxidize the PuO molecule? Mechanisms, topological analysis and rate constant calculations

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Systematic analysis of structural and topological properties: new insights into PuO2(H2O)n2+(n = 1–6) complexes in the gas phase

Abstract: In this study, the equilibrium, electronic structures, bonding and topological properties of PuO2(H2O)n2+ (n = 1–6) complexes were systematically investigated.

Cited by 10 publications

References 54 publications

Quantum chemical study of reaction mechanism between plutonium and nitrogen

Quantum chemical study of reaction mechanism between plutonium and nitrogen

HMNTA Complexes of Tetravalent Metal Ions: On the Roles of Carbonyl Oxygen and Amine Nitrogen in the Stabilization of Gas-Phase M(HMNTA)24+Complexes

Can water continuously oxidize the PuO molecule? Mechanisms, topological analysis and rate constant calculations

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Systematic analysis of structural and topological properties: new insights into PuO₂(H₂O)_n²⁺(n = 1–6) complexes in the gas phase

HMNTA Complexes of Tetravalent Metal Ions: On the Roles of Carbonyl Oxygen and Amine Nitrogen in the Stabilization of Gas-Phase M(HMNTA)₂⁴⁺Complexes