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Theoretical Examination of Covalency in Berkelium(IV) Carbonate Complexes
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  • Cristian Celis-Barros,
  • David Hobart,
  • Dayán Páez-Hernández,
  • Thomas Albrech-Schmitt
Cristian Celis-Barros
Florida State University
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David Hobart
Florida State University
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Dayán Páez-Hernández
Universidad Andres Bello
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Thomas Albrech-Schmitt
Florida State University
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Abstract

Experimental studies on the speciation of berkelium in carbonate media have shown that complexation of berkelium(III) by carbonate results in spontaneous oxidation to berkelium(IV) and that multiple species can be present in solution. We studied two proposed structures present in solution based on theoretical comparisons with spectroscopic data previously reported for Bk(IV) carbonate solutions. The multiconfigurational character of the ground and low-lying excited states in both complexes is demonstrated to result from the strong spin-orbit coupling. Although bonding in berkelium(IV) carbonate and carbonate-hydroxide complexes is dominated by strong Coulombic forces, the presence of the non-negligible covalent character is supported by ligand-field theory, natural localized orbitals and topological studies of the electron density. Bond orders based in natural localized molecular orbitals (NLMOs) show that Bk–OH bonds possess enhanced orbital overlap that is reflected in the bond strength.

Peer review status:ACCEPTED

28 Jan 2020Submitted to International Journal of Quantum Chemistry
29 Jan 2020Submission Checks Completed
29 Jan 2020Assigned to Editor
31 Jan 2020Reviewer(s) Assigned
13 Feb 2020Review(s) Completed, Editorial Evaluation Pending
14 Feb 2020Editorial Decision: Revise Major
13 Mar 20201st Revision Received
13 Mar 2020Submission Checks Completed
13 Mar 2020Assigned to Editor
16 Mar 2020Reviewer(s) Assigned
30 Mar 2020Review(s) Completed, Editorial Evaluation Pending
01 Apr 2020Editorial Decision: Accept