Emergence of californium as the second transitional element in the actinide series

Samantha K. Cary, Monica Vasiliu, Ryan E. Baumbach, Jared T. Stritzinger, Thomas D. Green, Kariem Diefenbach, Justin N. Cross, Kenneth L. Knappenberger, Guokui Liu, Mark A. Silver, A. Eugene DePrince, Matthew J. Polinski, Shelley M. Van Cleve, Jane H. House, Naoki Kikugawa, Andrew Gallagher, Alexandra A. Arico, David A. Dixon and Thomas E. Albrecht-Schmitt ()
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Samantha K. Cary: Florida State University
Monica Vasiliu: The University of Alabama
Ryan E. Baumbach: National High Magnetic Field Laboratory
Jared T. Stritzinger: Florida State University
Thomas D. Green: Florida State University
Kariem Diefenbach: Florida State University
Justin N. Cross: Florida State University
Kenneth L. Knappenberger: Florida State University
Guokui Liu: Argonne National Laboratory
Mark A. Silver: Florida State University
A. Eugene DePrince: Florida State University
Matthew J. Polinski: Florida State University
Shelley M. Van Cleve: Nuclear Materials Processing Group, Oak Ridge National Laboratory
Jane H. House: Florida State University
Naoki Kikugawa: National Institute for Materials Science
Andrew Gallagher: National High Magnetic Field Laboratory
Alexandra A. Arico: Florida State University
David A. Dixon: The University of Alabama
Thomas E. Albrecht-Schmitt: Florida State University

Nature Communications, 2015, vol. 6, issue 1, 1-8

Abstract: Abstract A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. The metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.

Date: 2015
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DOI: 10.1038/ncomms7827

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