Evidence of Alpha Radiolysis in the Formation of a Californium Nitrate Complex

Shane S Galley; Carlo Alberto Gaggioli; Matthias Zeller; Cristian Celis-Barros; Thomas E Albrecht-Schmitt; Laura Gagliardi; Suzanne C Bart

doi:10.1002/chem.202001904

Evidence of Alpha Radiolysis in the Formation of a Californium Nitrate Complex

Chemistry. 2020 Jul 22;26(41):8885-8888. doi: 10.1002/chem.202001904. Epub 2020 Jul 8.

Authors

Shane S Galley¹, Carlo Alberto Gaggioli², Matthias Zeller¹, Cristian Celis-Barros³, Thomas E Albrecht-Schmitt³, Laura Gagliardi², Suzanne C Bart¹

Affiliations

¹ H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana, 47907, USA.
² Department of Chemistry, Supercomputing Institute, and Chemical Theory Center, University of Minnesota, Minneapolis, Minnesota, 55455, USA.
³ Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida, 32306, USA.

PMID: 32315469
DOI: 10.1002/chem.202001904

Abstract

Well-characterized complexes of transplutonium elements are scarce because of the experimental challenges of working with these elements and the rarity of the isotopes. This leads to a lack of structural and spectroscopic data needed to understand the nature of chemical bonds in these compounds. In this work, the synthesis of Cf(DOPO^q )₂ (NO₃ )(py) (DOPO^q =2,4,6,8-tetra-tert-butyl-1-oxo-1H-phenoxazin-9-olate; py=pyridine) is reported, in which the nitrate anion is hypothesized to form through the α-radiolysis-induced reaction of pyridine and/or the ligand. Computational analysis of the electronic structure of the complex reveals that the Cf^III -ligand interactions are largely ionic.

Keywords: californium; electronic structure analysis; f-element; radiolysis.

Abstract

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