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; Thomas E. Albrecht-Schmitt

doi:10.1038/ncomms7827

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, Thomas E. Albrecht-Schmitt

Research output: Contribution to journal › Article › peer-review

105 Scopus citations

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.

Original language	English
Article number	6827
Journal	Nature Communications
Volume	6
DOIs	https://doi.org/10.1038/ncomms7827
State	Published - Apr 16 2015
Externally published	Yes

Funding

This material is based on work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Heavy Elements Chemistry Program, under Award Number DE-FG02-13ER16414 (TEA-S) and DE-AC02-06CH11357 (GL and DAD). We are especially grateful for the assistance and supervision by the Office of Environmental Health and Safety at FSU; specifically Jason A. Johnson and Ashley L. Gray of the Office of Radiation Safety for their facilitation of these studies. D.A.D. thanks the Robert Ramsay Chair Fund of The University of Alabama for partial support. The isotopes used in this research were supplied by the U.S. Department of Energy, Office of Science, by the Isotope Program in the Office of Nuclear Physics. The 243Am, 248Cm and 249Cf were provided to Florida State University via the Isotope Development and Production for Research and Applications Program through the Radiochemical Engineering and Development Center at Oak Ridge National Laboratory. The 249Cf was purchased via the Gregory R. Choppin Chair Endowment. Magnetization measurements using the VSM SQUID MPMS were performed at the National High Magnetic Field Laboratory, which is supported by National Science Foundation Cooperative Agreement No. DMR-1157490, the State of Florida, and the U.S. Department of Energy.

Funders	Funder number
State of Florida
TEA-S	DE-AC02-06CH11357
National Science Foundation	DMR-1157490
U.S. Department of Energy
Directorate for Mathematical and Physical Sciences	1157490
Office of Science
Basic Energy Sciences	DE-FG02-13ER16414
Nuclear Physics
University of Alabama

Access to Document

10.1038/ncomms7827

Cite this

Cary, S. K., Vasiliu, M., Baumbach, R. E., Stritzinger, J. T., Green, T. D., Diefenbach, K., Cross, J. N., Knappenberger, K. L., Liu, G., Silver, M. A., Deprince, A. E., Polinski, M. J., Van Cleve, S. M., House, J. H., Kikugawa, N., Gallagher, A., Arico, A. A., Dixon, D. A., & Albrecht-Schmitt, T. E. (2015). Emergence of californium as the second transitional element in the actinide series. Nature Communications, 6, Article 6827. https://doi.org/10.1038/ncomms7827

@article{72661c6c0a96457d81560e6f92c015a7,

title = "Emergence of californium as the second transitional element in the actinide series",

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.",

author = "Cary, {Samantha K.} and Monica Vasiliu and Baumbach, {Ryan E.} and Stritzinger, {Jared T.} and Green, {Thomas D.} and Kariem Diefenbach and Cross, {Justin N.} and Knappenberger, {Kenneth L.} and Guokui Liu and Silver, {Mark A.} and Deprince, {A. Eugene} and Polinski, {Matthew J.} and {Van Cleve}, {Shelley M.} and House, {Jane H.} and Naoki Kikugawa and Andrew Gallagher and Arico, {Alexandra A.} and Dixon, {David A.} and Albrecht-Schmitt, {Thomas E.}",

year = "2015",

month = apr,

day = "16",

doi = "10.1038/ncomms7827",

language = "English",

volume = "6",

journal = "Nature Communications",

issn = "2041-1723",

publisher = "Nature Research",

}

Cary, SK, Vasiliu, M, Baumbach, RE, Stritzinger, JT, Green, TD, Diefenbach, K, Cross, JN, Knappenberger, KL, Liu, G, Silver, MA, Deprince, AE, Polinski, MJ, Van Cleve, SM, House, JH, Kikugawa, N, Gallagher, A, Arico, AA, Dixon, DA & Albrecht-Schmitt, TE 2015, 'Emergence of californium as the second transitional element in the actinide series', Nature Communications, vol. 6, 6827. https://doi.org/10.1038/ncomms7827

TY - JOUR

T1 - Emergence of californium as the second transitional element in the actinide series

AU - Cary, Samantha K.

AU - Vasiliu, Monica

AU - Baumbach, Ryan E.

AU - Stritzinger, Jared T.

AU - Green, Thomas D.

AU - Diefenbach, Kariem

AU - Cross, Justin N.

AU - Knappenberger, Kenneth L.

AU - Liu, Guokui

AU - Silver, Mark A.

AU - Deprince, A. Eugene

AU - Polinski, Matthew J.

AU - Van Cleve, Shelley M.

AU - House, Jane H.

AU - Kikugawa, Naoki

AU - Gallagher, Andrew

AU - Arico, Alexandra A.

AU - Dixon, David A.

AU - Albrecht-Schmitt, Thomas E.

PY - 2015/4/16

Y1 - 2015/4/16

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=84928041750&partnerID=8YFLogxK

U2 - 10.1038/ncomms7827

DO - 10.1038/ncomms7827

M3 - Article

AN - SCOPUS:84928041750

SN - 2041-1723

VL - 6

JO - Nature Communications

JF - Nature Communications

M1 - 6827

ER -

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

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this