Mononuclear thorium halide clusters ThX<sub>4</sub> (X = F, Cl): gas-phase hydrolysis reactions

Wang, Bin; Xia, Chan-Juan; Fang, Hong-Lin; Chen, Wen-Jie; Zhang, Yongfan; Huang, Xin

doi:10.1039/c8cp03071e

Cited by 6 publications

(4 citation statements)

References 59 publications

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“…Instead, temperature effects are accounted for by using the Boltzmann probability. Our probability formulation is based on how coordinating species can stabilize a central atom. − This change in energy is reflected in the per-atom formation enthalpy of a compound or a cluster. The probability, P i , of a metal atom i having any CN in a structure with per-atom formation enthalpy E i is where T is the temperature in Kelvin, k B is the Boltzmann constant, and E j is the per-atom formation enthalpy for the set of the metal center structure.…”

Section: Methodsmentioning

confidence: 99%

Modeling Metallic Halide Local Structures in Salt Melts Using a Genetic Algorithm

et al. 2022

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Knowing the local structure of metal ions in molten salt melts is essential for understanding the chemistry related to corrosion and solvation processes for various applications such as molten salt reactors, solar thermal power systems, and molten salt-enabled materials processing. However, modeling the dynamic local structure of metals in salt melts is difficult because classical mechanics does not reproduce the correct local atomic networking. The computational cost of carrying out multiple first-principles dynamics calculations to ensure that the compositional space is well sampled can be prohibitively large. In order to address this issue, the current study explores the use of the evolutionary algorithm Universal Structure Predictor: Evolutionary Xtallography (USPEX) to predict coordination numbers of strontium and zirconium in binary and ternary chloride and fluoride melts. Temperature-dependent coordination number distributions for the metal atoms were computed using a Boltzmann distribution. The calculated average coordination numbers were found to be consistent with observations from extended X-ray absorption fine structure (EXAFS) experiments and the expected temperature trends. Furthermore, the most stable predicted crystal structures compare well with EXAFS values, validating our approach for predicting local structures in salt melts.

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Section: Methodsmentioning

confidence: 99%

Modeling Metallic Halide Local Structures in Salt Melts Using a Genetic Algorithm

et al. 2022

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“…We have constantly strived to explore the novel chemical bonding of gas-phase clusters and to gain further insights into the active sites of complicated catalyst surfaces and the reaction mechanisms of catalytic processes [23][24][25][26]. As mentioned above, the sintering and aggregation of the supported Cu nano-particles are among the deactivation reasons for Cubased catalyst [2]; whereas small-sized supported Cu clusters possess high activity in some reactions [14].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on the Structures and Stabilities of CunZn3O3 (n = 1–4) Clusters: Sequential Doping of Zn3O3 Cluster with Cu Atoms

Tao,

Zou,

et al. 2024

Inorganics

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Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are performed to investigate the geometric and electronic structures and chemical bonding of a series of Cu-doped zinc oxide clusters: CunZn3O3 (n = 1–4). The structural evolution of CunZn3O3 (n = 1–4) clusters may reveal the aggregation behavior of Cu atoms on the Zn3O3 cluster. The planar seven-membered ring of the CuZn3O3 cluster plays an important role in the structural evolution; that is, the Cu atom, Cu dimer (Cu2) and Cu trimer (Cu3) anchor on the CuZn3O3 cluster. Additionally, it is found that CunZn3O3 clusters become more stable as the Cu content (n) increases. Bader charge analysis points out that with the doping of Cu atoms, the reducibility of Cu aggregation (Cun−1) on the CuZn3O3 cluster increases. Combined with the d-band centers and the surface electrostatic potential (ESP), the reactivity and the possible reaction sites of CunZn3O3 (n = 1–4) clusters are also illustrated.

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“…Adjusting the oxygen content of oxides often bring about the oxygen‐deficient site and the other reactive oxygen species, together with changing their chemical behaviour [37–41] . It is worth mentioning that thorium has the completely empty 5 f orbital ([Rn] 6 d 2 7 s 2 ), [42] which has similar valence electron configuration to the group IVB transition metal instead of the other actinide metals. In this view, thorium seems to resemble the group IVB metal elements to some extent.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Thorium Oxide Clusters with Water: The Effects of Oxygen Content

Wang

Zhang

et al. 2022

ChemPhysChem

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Thorium oxide has many important applications in industry. In this article, theoretical calculations have been carried out to explore the hydrolysis reactions of the ThO n (n = 1-3) clusters. The reaction mechanisms of the O-deficient ThO and the O-rich ThO 3 are compared with the stoichiometric ThO 2 . The theoretical results show good agreement with the prior experiments. It is shown that the hydrolysis mainly occurred on the singlet potential surface. The overall reactions consist of two hydrolysis steps which are all favourable in energy. The effects of oxygen content on the hydrolysis are elucidated. Interestingly, among them, the peroxo group O 2 2À in ThO 3 is converted to the HOOÀ ligand, behaving like the terminal O 2À in the hydrolysis which is transformed into the HOÀ groups. In addition, natural bond orbital (NBO) analyses were employed to further understand the bonding of the pertinent species and to interpret the differences in hydrolysis.

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Mononuclear thorium halide clusters ThX₄ (X = F, Cl): gas-phase hydrolysis reactions

Cited by 6 publications

References 59 publications

Modeling Metallic Halide Local Structures in Salt Melts Using a Genetic Algorithm

Modeling Metallic Halide Local Structures in Salt Melts Using a Genetic Algorithm

Theoretical Study on the Structures and Stabilities of CunZn3O3 (n = 1–4) Clusters: Sequential Doping of Zn3O3 Cluster with Cu Atoms

Reactions of Thorium Oxide Clusters with Water: The Effects of Oxygen Content

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Mononuclear thorium halide clusters ThX4 (X = F, Cl): gas-phase hydrolysis reactions

Cited by 6 publications

References 59 publications

Modeling Metallic Halide Local Structures in Salt Melts Using a Genetic Algorithm

Modeling Metallic Halide Local Structures in Salt Melts Using a Genetic Algorithm

Theoretical Study on the Structures and Stabilities of CunZn3O3 (n = 1–4) Clusters: Sequential Doping of Zn3O3 Cluster with Cu Atoms

Reactions of Thorium Oxide Clusters with Water: The Effects of Oxygen Content

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Mononuclear thorium halide clusters ThX₄ (X = F, Cl): gas-phase hydrolysis reactions