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Bonding of isovalent homologous actinide and lanthanide pairs with chalcogenide donors: effect of metal f-orbital participation and donor softness

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Abstract

Chemistry of f-element gains importance in several fields due to the extensive scope of their applications. The aim of this study is to understand the subtle differences in bonding in the structurally similar actinides (An) and their homologous (isovalent) lanthanides (Ln) with several donors, which may lead to their covalency mediated separation. Several experimental and theoretical studies have been reported to address this aspect. However, to the best of our knowledge, a systematic study on the variation in the bonding patterns of the isovalent ‘Ln’ and ‘An’ pairs encompassing the effect of valence f-orbital participation was not attempted. In this study, the minute differences in covalent interactions of these An/Ln pairs having same number of f-electrons with chalcogenide ions of varying softness was probed using relativistic density functional theory (DFT). The f-electronic configurations of the metal ions were observed to play an important role in the f-orbital participation. [AnX]+/[LnX]+ pairs with f0, f7 (half-filled) configurations show resistance to f-orbital directed bonding, unlike the systems having f5, f6 electronic configurations where the f-orbital directed covalency is more pronounced in the [AnX]+ systems. The nature of covalency was identified to be near degeneracy-driven. This enhanced covalency was found to increase with the subsequent increase in the softness of the donor centres.

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Acknowledgements

SC acknowledges the unceasing encouragement provided by Dr. M. S. Kulkarni, Head, Health Physics Division, BARC. Authors are grateful to Dr. Ashokkumar P. (Group Leader, HP Unit, RLG, BARC), Shri R. V. Kolekar (Head, RPS-SF, BARC), Dr. P. K. Mohapatra (Head, RCD, BARC) and Dr. S. Kannan (Director, RC & I Group and Head FCD, BARC). Authors also thank ANUPAM Supercomputing Facility, Bhabha Atomic Research Center, India for the computational resources.

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Authors and Affiliations

  1. Health Physics Division, Health, Safety and Environment Group, Bhabha Atomic Research Centre, Mumbai, 400 085, India

    Saparya Chattaraj

  2. Radiochemistry Division, Radiochemistry and Isotope Group, Bhabha Atomic Research Centre, Mumbai, 400 085, India

    Arunasis Bhattacharyya

  3. Homi Bhabha National Institute, Mumbai-400 094, Anushaktinagar, India

    Saparya Chattaraj & Arunasis Bhattacharyya

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  1. Saparya Chattaraj
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  2. Arunasis Bhattacharyya
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Saparya Chattaraj: data curation, formal analysis, investigation, methodology, validation, visualization, writing—original draft; Arunasis Bhattacharyya: conceptualization, investigation, methodology, resources, supervision, writing—review and editing.

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Correspondence to Arunasis Bhattacharyya.

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Chattaraj, S., Bhattacharyya, A. Bonding of isovalent homologous actinide and lanthanide pairs with chalcogenide donors: effect of metal f-orbital participation and donor softness. Struct Chem 34, 307–316 (2023). https://doi.org/10.1007/s11224-022-02094-9

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