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Ab initio predictions for the reaction mechanism and orbital topological properties of the formation of Neptunimine, Plutonimine, and its side products

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Abstract

Exploring the different mechanisms involved in the application of actinide is necessary to obtain a more comprehensive understanding of actinide science. In this study, the mechanisms of gas-phase Np and Pu atoms dissociating NH3 molecules forming Neptunimine and Plutonimine complexes were systematically investigated using different approaches of density functional theory. A new dehydrogenation channel was discovered. The results reveal that the intermediates HAn-NH2 are the lowest energy in the overall reaction, and the direct planar evolution dehydrogenations are the lowest energy reaction path. Besides, the mechanism of the initial complexation process is discussed on the electron localization function, atoms-in-molecules, atomic dipole moment corrected Hirshfeld atomic charges, and electron density difference analysis. The results indicate that An-N in complex I exhibits a very weak covalent interaction, and it comes down to pulling the original dipole moment of the NH3 molecule and stretched between An atom and three H atoms.

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Acknowledgments

We are very grateful to Dr. Sobereva for many helpful discussions and providing us with the Multiwfn package.

Funding

This work is supported by National Natural Science Foundation of China (NSFC) (Grant No. 11604187, 11647040, 61722507, 61675121, 61705123), the Natural Science Young Foundation of Shanxi Province (Grant No. 201801D221004), the Cooperation projects of Institute of Applied Physics and Computational Mathematics, and Open Fund of Key Laboratory of Advanced Reactor Engineering and Safety, Ministry of Education (Tsinghua University, China), The Program for the Outstanding Innovative Teams of Higher Learning Institutions of Shanxi.

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Authors and Affiliations

  1. School of Physics and Electronics Engineering, State Key Laboratory of Quantum Optics and Quantum Optics Devices, Laser Spectroscopy Laboratory, Shanxi University, Taiyuan, 030006, China

    Peng Li, Jizhou Wu, Yuqing Li, Wenliang Liu, Yongming Fu & Jie Ma

  2. Department of Physics, Taiyuan Normal University, Taiyuan, 030031, China

    Wenxia Niu

  3. Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan, 030006, China

    Jizhou Wu, Yuqing Li, Wenliang Liu & Jie Ma

  4. Institute of Nuclear and New Energy Technology, Collaborative Innovation Center of Advanced Nuclear Energy Technology, Key Laboratory of Advanced Reactor Engineering and Safety of Ministry of Education, Tsinghua University, Beijing, 100084, China

    Feng Xie

  5. Institute of Applied Physics and Computational Mathematics, Beijing, 100088, China

    Yong Wu

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  1. Peng Li
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Correspondence to Peng Li or Jie Ma.

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Li, P., Niu, W., Wu, J. et al. Ab initio predictions for the reaction mechanism and orbital topological properties of the formation of Neptunimine, Plutonimine, and its side products. J Mol Model 26, 163 (2020). https://doi.org/10.1007/s00894-020-04424-2

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  • DOI: https://doi.org/10.1007/s00894-020-04424-2

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