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

Author

Listed:
  • 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)

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.

Suggested Citation

  • 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, 2015. "Emergence of californium as the second transitional element in the actinide series," Nature Communications, Nature, vol. 6(1), pages 1-8, November.
    • Handle: RePEc:nat:natcom:v:6:y:2015:i:1:d:10.1038_ncomms7827
    DOI: 10.1038/ncomms7827
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    Cited by:

    1. Alyssa N. Gaiser & Cristian Celis-Barros & Frankie D. White & Maria J. Beltran-Leiva & Joseph M. Sperling & Sahan R. Salpage & Todd N. Poe & Daniela Gomez Martinez & Tian Jian & Nikki J. Wolford & Nat, 2021. "Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    2. Brian N. Long & María J. Beltrán-Leíva & Joseph M. Sperling & Todd N. Poe & Cristian Celis-Barros & Thomas E. Albrecht-Schönzart, 2023. "Altering the spectroscopy, electronic structure, and bonding of organometallic curium(III) upon coordination of 4,4′−bipyridine," Nature Communications, Nature, vol. 14(1), pages 1-9, December.

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