Chemical characterization of heavy actinides and light transactinides - Experimental achievements at JAEA.

The chemical characterization of the heaviest elements at the farthest reach of the periodic table (PT) and the classification of these elements in the PT are undoubtedly crucial and challenging subjects in chemical and physical sciences. The elucidation of the influence of relativistic effects on their outermost electronic configuration is also a critical and fascinating aspect. However, the heaviest elements with atomic numbers Z ≳ 100 must be produced at accelerators using nuclear reactions of heavy ions and target materials. Therefore, production rates for these elements are low, and their half-lives are as short as a few seconds to a few minutes; they are usually available in a quantity of only a few atoms at a time. Here, we review some highlighted studies on heavy actinide and light transactinide chemical characterization performed at the Japan Atomic Energy Agency tandem accelerator facility. We discuss briefly the prospects for future studies of the heaviest elements.

Correction: Novel 90Sr analysis of environmental samples by Ion-Laser InterAction Mass Spectrometry.

Correction for 'Novel 90Sr analysis of environmental samples by Ion-Laser InterAction Mass Spectrometry' by Maki Honda et al., Anal. Methods, 2022, 14, 2732-2738, https://doi.org/10.1039/D2AY00604A.

Novel 90Sr analysis of environmental samples by Ion-Laser InterAction Mass Spectrometry.

The sensitive analysis of 90Sr with accelerator mass spectrometry (AMS) was developed to advance environmental radiology. One advantage of AMS is the ability to analyze environmental samples with 90Sr/88Sr atomic ratios of 10-14 in following a simple chemical separation. Three different IAEA samples with known 90Sr concentrations (moss-soil, animal bone, Syrian soil: 1 g each) were analyzed to assess the validity of the chemical separation and the AMS measurement. The 90Sr measurements were conducted on the AMS system VERA combined with the Ion Laser InterAction Mass Spectrometry (ILIAMS) setup at the University of Vienna, which has excellent isobaric separation performance. The isobaric interference of 90Zr in the 90Sr AMS was first largely removed by chemical separation. The separation factor of Zr in two-step column chromatography with Sr resin and anion exchange resin was 106. The 90Zr remaining in the sample was effectively suppressed by ILIAMS. This procedure achieved a limit of detection <0.1 mBq in the 90Sr AMS, which is lower than typical ß-ray detection. The agreement between AMS measurements and nominal values for the 90Sr concentrations of IAEA samples indicated that the new highly-sensitive 90Sr analysis in the environmental samples with AMS is reliable.

Chemical Characterization of a Volatile Dubnium Compound, DbOCl3.

The formation and the chemical characterization of single atoms of dubnium (Db, element 105), in the form of its volatile oxychloride, was investigated using the on-line gas phase chromatography technique, in the temperature range 350-600 °C. Under the exactly same chemical conditions, comparative studies with the lighter homologues of Group 5 in the Periodic Table clearly indicate the volatility sequence being NbOCl3 > TaOCl3 ≥ DbOCl3 . From the obtained experimental results, thermochemical data for DbOCl3 were derived. The present study delivers reliable experimental information for theoretical calculations on chemical properties of transactinides.

First Ionization Potentials of Fm, Md, No, and Lr: Verification of Filling-Up of 5f Electrons and Confirmation of the Actinide Series.

We report the first ionization potentials (IP1) of the heavy actinides, fermium (Fm, atomic number Z = 100), mendelevium (Md, Z = 101), nobelium (No, Z = 102), and lawrencium (Lr, Z = 103), determined using a method based on a surface ionization process coupled to an online mass separation technique in an atom-at-a-time regime. The measured IP1 values agree well with those predicted by state-of-the-art relativistic calculations performed alongside the present measurements. Similar to the well-established behavior for the lanthanides, the IP1 values of the heavy actinides up to No increase with filling up the 5f orbital, while that of Lr is the lowest among the actinides. These results clearly demonstrate that the 5f orbital is fully filled at No with the [Rn]5f147s2 configuration and that Lr has a weakly bound electron outside the No core. In analogy to the lanthanide series, the present results unequivocally verify that the actinide series ends with Lr.

Measurement of the Md3+/Md2+ reduction potential studied with flow electrolytic chromatography.

The reduction behavior of mendelevium (Md) was studied using a flow electrolytic chromatography apparatus. By application of the appropriate potentials on the chromatography column, the more stable Md(3+) is reduced to Md(2+). The reduction potential of the Md(3+) + e(-) → Md(2+) couple was determined to be -0.16 ± 0.05 V versus a normal hydrogen electrode.

First successful ionization of Lr (Z = 103) by a surface-ionization technique.

We have developed a surface ionization ion-source as part of the JAEA-ISOL (Isotope Separator On-Line) setup, which is coupled to a He/CdI2 gas-jet transport system to determine the first ionization potential of the heaviest actinide lawrencium (Lr, Z = 103). The new ion-source is an improved version of the previous source that provided good ionization efficiencies for lanthanides. An additional filament was newly installed to give better control over its operation. We report, here, on the development of the new gas-jet coupled surface ion-source and on the first successful ionization and mass separation of 27-s (256)Lr produced in the (249)Cf + (11)B reaction.