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The oxo exchange reaction mechanism of americyl(VI): a density functional theory study

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Abstract

This work concerned the oxo exchange of americyl(VI) ([AmO2]2+) in alkaline solution by means of B3LYP calculations. Four possible reaction pathways were investigated and compared, which covered the direct intramolecular proton transfer pathway (Path 1 and 2), the pathway via a T-shape [AmO3](aq) intermediate (Path 3), and the binuclear pathway (Path 4). The Path 3 was predicted as the most probable pathway in view of the energetics, the activation energy (∆G≠) to which was calculated to be 55.7 kJ/mol. The evolution of the Mayer bond order of key bonds were analyzed to assist the understanding of the mechanism.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China to W. Chen (10676007), Z. Chai (91026000) and D. Wang (21473206 and 91226105), and the CAS Hundred Talents Program to D. Wang (Y2291810S3), which are gratefully acknowledged. Calculations were done on the computational grids in the National Supercomputing Center in Tianjin (NSCC-TJ).

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Authors and Affiliations

  1. College of Chemistry, Fuzhou University, Fuzhou, 350108, Fujian, China

    Ciliang Xie & Wenkai Chen

  2. Multidisciplinary Initiative Center, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China

    Ciliang Xie, Zhifang Chai & Dongqi Wang

  3. State Key Laboratory of Radiation Medicine and Protection, School of Radiation Medicine and Interdisciplinary Sciences (RAD-X), Soochow University, Suzhou, 215123, Jiangsu, China

    Zhifang Chai

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  1. Ciliang Xie
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10967_2020_7097_MOESM1_ESM.docx

Supplementary information SI_1: the values of < S2 > after annihilation for monomeric and dimeric complexes or transition states, the Mulliken atomic charges (Table S4 and S5), the key chemical bond order of the species along the Path 3 and 4, the electronic localization function (ELF) of key species along Path 4, and the coordinates of all stationary points. SI_2: our latest calculations for the Path 3 of neptunyl(VI) in alkaline solution. (DOCX 17063 kb)

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Xie, C., Chen, W., Chai, Z. et al. The oxo exchange reaction mechanism of americyl(VI): a density functional theory study. J Radioanal Nucl Chem 324, 857–868 (2020). https://doi.org/10.1007/s10967-020-07097-6

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