Contemporary Chemistry of Berkelium and Californium

White, Frankie D.; Dan, David; Albrecht‐Schmitt, Thomas E.

doi:10.1002/chem.201900586

Contemporary Chemistry of Berkelium and Californium

Journal Article · Mon Mar 25 00:00:00 EDT 2019 · Chemistry - A European Journal

DOI:https://doi.org/10.1002/chem.201900586· OSTI ID:2346199

White, Frankie D. ^[1]; Dan, David ^[2]; ^[2]

Florida State Univ., Tallahassee, FL (United States); Florida State University
Florida State Univ., Tallahassee, FL (United States)

The merging of small-scale syntheses and rapid crystallization methods have provided access to crystalline samples of berkelium (Z=97) and californium (Z=98) coordination complexes and compounds that can be interrogated with a suite of spectroscopic tools and structural elucidation approaches that have come online over the last 20 years. The combination of this experimental data with relativistic theoretical methods that capture the effects of spin-orbit coupling and scalar relativistic effects have allowed us to understand the electronic structure of berkelium and californium compounds at a level of detail that was not previously possible. The harbinger of this new era of post-curium chemistry was the synthesis and characterization of [Cf{B₆O₈(OH)₅}]. This compound possesses a structure type that is distinct from earlier actinide borates, a reduction in coordination number for californium, contracted Cf-O bond lengths, a substantially reduced magnetic moment with respect to the calculated free-ion moment and, most importantly, vibronically coupled broadband photoluminescence. Ligand-field analysis also showed that the splitting of the ground state was larger than typically found in the f-block elements, and when taken together places its overall electronic structure as a hybrid of d- and f-block components. The discovery of the unusual properties of this compound has led to the development of large families of 4f and 5f coordination complexes, in an effort to uncover the underlying origin of the electronic structure oddities, and whether there really is a sharp onset of these changes at californium. This in turn pushed the development of far more challenging berkelium chemistry (from a radiologic standpoint) because the half-life of the isotopes decreases from 351 years for ²⁴⁹Cf to 330 days for ²⁴⁹Bk. This short review details some of the chemistry that has been reported over the last 15 years, and its consequences for understanding the periodic table.

View Accepted Manuscript (DOE)

Research Organization:: Florida State Univ., Tallahassee, FL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0010677

OSTI ID:: 2346199

Alternate ID(s):: OSTI ID: 1525551
OSTI ID: 22972098

Journal Information:: Chemistry - A European Journal, Journal Name: Chemistry - A European Journal Journal Issue: 44 Vol. 25; ISSN 0947-6539

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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