On the existence of divalent californium in aqueous solution

Cohen, Leo H.; Aten, A.H.W.; Kooi, J.

doi:10.1016/0020-1650(68)80123-0

Cited by 13 publications

(9 citation statements)

References 5 publications

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“…[52,53] In the + II state these studies provide important comparisons with Sm II , which is the closeste lectrochemical analog of Cf II ,a nd similar gas-phase speciation was observed for Sm II and Cf II complexes. [54,55] Albeit, divalent californium chemistry has been historically somewhat developed in simple binary compounds such as halides, little else is known about californium's divalent character. [21,54] Studies of the pentavalent states revealed more non-intuitive trends in which covalency in the An=Ob onds from Pu V to Cf V is observed across the actinide series concomitant with distortions of the linear geometry of AnO 2 + cation from the linear, trans-PuO 2 + cation to bents tructures for AmO 2 + ,C mO 2 + ,a nd BkO 2 + ,a nd finally to a cis-geometryf or CfO 2 + as shown in Figure 4.…”

Section: Solutiona Nd Gas-phase Studies Of Californiummentioning

confidence: 99%

“…[54,55] Albeit, divalent californium chemistry has been historically somewhat developed in simple binary compounds such as halides, little else is known about californium's divalent character. [21,54] Studies of the pentavalent states revealed more non-intuitive trends in which covalency in the An=Ob onds from Pu V to Cf V is observed across the actinide series concomitant with distortions of the linear geometry of AnO 2 + cation from the linear, trans-PuO 2 + cation to bents tructures for AmO 2 + ,C mO 2 + ,a nd BkO 2 + ,a nd finally to a cis-geometryf or CfO 2 + as shown in Figure 4. An inherentf eature of working with high-specific activity nuclei is radiolytic reactions that are particularly pronouncedi n aqueous media where ah ost of radiolytic products that in-clude hydroxyl radical, hydrogen atoms, hydrogen peroxide, oxygen atoms, and hydroperoxyl will form.…”

Section: Solutiona Nd Gas-phase Studies Of Californiummentioning

confidence: 99%

“…Gas‐phase studies on californium complexes have been used to investigate all oxidation states from Cf II to Cf V . In the +II state these studies provide important comparisons with Sm II , which is the closest electrochemical analog of Cf II , and similar gas‐phase speciation was observed for Sm II and Cf II complexes . Albeit, divalent californium chemistry has been historically somewhat developed in simple binary compounds such as halides, little else is known about californium's divalent character .…”

Section: Californiummentioning

confidence: 99%

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Contemporary Chemistry of Berkelium and Californium

White

Dan

Albrecht‐Schönzart

2019

Chemistry A European J

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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.

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Section: Solutiona Nd Gas-phase Studies Of Californiummentioning

confidence: 99%

Section: Solutiona Nd Gas-phase Studies Of Californiummentioning

confidence: 99%

Section: Californiummentioning

confidence: 99%

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Contemporary Chemistry of Berkelium and Californium

White

Dan

Albrecht‐Schönzart

2019

Chemistry A European J

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“…The redox solution chemistry of Sm 3 þ and Cf 3 þ ions should be similar, as indicated by standard reduction potentials to the ground state of À 2.3 V and À 1.94 V, respectively (although it should not be assumed that the [5]. Even though Dy is the electronic homolog to Cf, and Gd is closer to Cf in cationic radius, it has been suggested that Sm, like Cf, has a (transient) divalent state in acid solution between the trivalent and ground states [6,7]. It has also been shown via co-precipitation studies in various solvents that the reduction behavior of Cf will closely follow Sm [8].…”

Section: Introductionmentioning

confidence: 94%

Electrodeposition of actinide compounds from an aqueous ammonium acetate matrix: Experimental development and optimization

Torrico

Boll

Matoš

2015

Nuclear Instruments and Methods in Physics Research Section A:

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a b s t r a c tElectrodeposition is a technique routinely employed in nuclear research for the preparation of thin solid films of actinide materials used in accelerator beam bombardments, irradiation studies, or as radioactive sources. This study investigates the deposition of both lanthanides and actinides from an aqueous ammonium acetate electrolyte matrix. Electrodepositions were performed primarily on stainless steel disks, with yield analysis evaluated using γ-spectroscopy. Experimental parameters (run time, current density, voltage, electrolyte concentration, and initial analyte mass) were studied and modified to optimize the uniformity and adherence of the deposition while maximizing yield. The procedure utilized samarium as the plating material, both with and without a radioactive tracer. Surface characterization studies were performed by scanning electron microscopy, electron microprobe analysis, radiographic imaging, and x-ray diffraction.

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“…3.4.1 New oxidation states of the actinide elements.-The work mentioned in Section 2.6.8 on the newly reported (VII) oxidation states of neptunium and plutonium (137)(138)(139)(140) and in Sections 2.1.3, 2.2.2, and 2.6.10 on the (II) oxidation states of several of the heavy actinide elements (67,83,84,98,(170)(171)(172)(173)(174)(175) focuses attention on the always interesting subject of the oxidation states of the actinide elements. As indicated in the following paragraphs, the limits of stability of oxidation states are related in a complicated way to the ionization potentials of the gaseous atoms.…”

Section: Interpretation and Prediction Of Chemical Behaviormentioning

confidence: 99%