Extreme chemistry of superheavy elements

Sato, Tetsuya; Nagame, Yuichiro*

Nihon Butsuri Gakkai-Shi, 78(2), p.64 - 72, 2023/02

https://doi.org/10.11316/butsuri.78.2_64

The study of the chemistry of superheavy elements, which are located in the heavy extremes of the periodic table, has made considerable progress over the past 20 years, and new approaches based on various ideas have recently been developed. Research groups in Japan have also made significant contributions to the development of research on superheavy elements. Recently, notable results have been reported for the transactinide elements rutherfordium (element 104), dubnium (element 105), and seaborgium (element 106), and the heavy actinides with atomic numbers exceeding 100. The review will focus on the recent main results of these elements. This review outlines the main recent results and touches on future prospects.

On the adsorption and reactivity of element 114, flerovium

Yakushev, A.*; Lens, L.*; Dllmann, Ch. E.*; Khuyagbaatar, J.*; Jger, E.*; Krier, J.*; Runke, J.*; Albers, H. M.*; Asai, Masato; Block, M.*; et al.

Frontiers in Chemistry (Internet), 10, p.976635_1 - 976635_11, 2022/08

https://doi.org/10.3389/fchem.2022.976635

Flerovium (Fl, element 114) is the heaviest element chemically studied so far. The first chemical experiment on Fl suggested that Fl is a noble-gas-like element, while the second studies suggested that Fl has a volatile-metal-like character. To obtain more reliable conclusion, we performed further experimental studies on Fl adsorption behavior on Si oxide and gold surfaces. The present results suggest that Fl is highly volatile and less reactive than the volatile metal, Hg, but has higher reactivity than the noble gas, Rn.

Application of a novel gas phase synthesis approach to carbonyl complexes of accelerator-produced 5d transition metals

Gtz, M.*; Yakushev, A.*; Gtz, S.*; Di Nitto, A.*; Dllmann, Ch. E.*; Asai, Masato; Kindler, B.*; Krier, J.*; Lommel, B.*; Nagame, Yuichiro*; et al.

Radiochimica Acta, 110(2), p.75 - 86, 2022/02

https://doi.org/10.1515/ract-2021-1028

The study of volatile superheavy element carbonyl complexes requires more efficient methods because the yield of transactinide elements decreases with increasing atomic number. This is achieved by using a newly developed double chamber system to separate the recoil chamber and the reaction one, thereby avoiding the decomposition of reactive molecules by the projectile ion beam, which hinders the synthesis of carbonyl complexes. The feasibility of this method was verified by synthesizing 5d metal short-lived isotopes as homologous element isotopes of the light transactinide elements Sg, Bh, Hs, and Mt at the Japan Atomic Energy Agency tandem accelerator and conducting model experiments.

Chemical characterization of a volatile dubnium compound, DbOCl

Chiera, N. M.*; Sato, Tetsuya; Eichler, R.*; Tomitsuka, Tomohiro; Asai, Masato; Adachi, Sadia*; Dressler, R.*; Hirose, Kentaro; Inoue, Hiroki*; Ito, Yuta; et al.

Angewandte Chemie; International Edition, 60(33), p.17871 - 17874, 2021/08

https://doi.org/10.1002/anie.202102808

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 exact same chemical conditions, comparative studies with the lighter homologs of group-5 in the Periodic Table clearly indicate the volatility sequence being NbOCl TaOCl DbOCl. From the obtained experimental results, thermochemical data for DbOCl were derived. The present study delivers reliable experimental information for theoretical calculations on the chemical properties of transactinides.

First online operation of TRIGA-TRAP

Grund, J.*; Asai, Masato; Blaum, K.*; Block, M.*; Chenmarev, S.*; Dllmann, Ch. E.*; Eberhardt, K.*; Lohse, S.*; Nagame, Yuichiro*; Nagy, Sz.*; et al.

Nuclear Instruments and Methods in Physics Research A, 972, p.164013_1 - 164013_8, 2020/08

https://doi.org/10.1016/j.nima.2020.164013

We report on the successful coupling of the Penning-trap mass spectrometry setup TRIGA-TRAP to the research reactor TRIGA Mainz. This offers the possibility to perform direct high-precision mass measurements of short-lived nuclei produced in neutron-induced fission of a U target located near the reactor core. An aerosol-based gas-jet system is used for efficient transport of short-lived neutron-rich nuclei from the target chamber to a surface ion source. In conjunction with new ion optics and extended beam monitoring capabilities, the experimental setup has been fully commissioned. The design of the surface ion source, efficiency studies and first results are presented.

Nuclear and chemical characterization of heavy actinides

Nagame, Yuichiro

Radiochimica Acta, 107(9-11), p.803 - 819, 2019/09

https://doi.org/10.1515/ract-2019-3133

Optimization of an isothermal gas-chromatographic setup for the chemical exploration of dubnium (Db, Z = 105) oxychlorides

Chiera, N. M.; Sato, Tetsuya; Tomitsuka, Tomohiro; Asai, Masato; Ito, Yuta; Shirai, Kaori*; Suzuki, Hayato; Tokoi, Katsuyuki; Toyoshima, Atsushi; Tsukada, Kazuaki; et al.

Journal of Radioanalytical and Nuclear Chemistry, 320(3), p.633 - 642, 2019/06

https://doi.org/10.1007/s10967-019-06505-w

An isothermal gas-chromatographic (IGC) device has been developed and tested for on-line gas phase studies of volatile oxychlorides of short-lived group-5 transition metals. Radioisotopes of niobium and tantalum, produced in nuclear fusion evaporation reactions, are directly flushed into the IGC setup by an inert gas-jet. Oxychloride compounds are formed by the addition of SOCl and O. Parameters influencing the formation and transport of NbOCl and TaOCl are investigated. For nuclides with half-lives () of about 30 s, an overall efficiency of 7% is obtained, rendering the IGC setup suitable for the chemical exploration of Db( = 34s).

Formation and thermochemical properties of oxychlorides of niobium (Nb) and tantalum (Ta); Towards the gas-phase investigation of dubnium (Db) oxychloride

Chiera, N. M.; Sato, Tetsuya; Tomitsuka, Tomohiro; Asai, Masato; Suzuki, Hayato*; Tokoi, Katsuyuki; Toyoshima, Atsushi; Tsukada, Kazuaki; Nagame, Yuichiro

Inorganica Chimica Acta, 486, p.361 - 366, 2019/02

https://doi.org/10.1016/j.ica.2018.10.032

The formation of NbOCl and TaOCl and their adsorption behavior on quartz surfaces was explored by applying an isothermal gas-chromatographic method. Trace amounts of short-lived Nb and Ta isotopes were used. Adsorption enthalpy values () at zero surface coverage of -(NbOCl) = 102 4 kJ/mol and -(TaOCl) = 128 5 kJ/mol were determined by analyzing the chromatographic behavior of the Nb andTa complexes with a Monte-Carlo simulation method based on an adsorption-desorption kinetic model.By applying an empirical correlation, the experimental values were successively related to the macroscopic standard sublimation enthalpy, , as a measure of the volatility of each substance. The inferred sublimation enthalpies are in agreement with tabulated thermochemical values. Thus, the linear empirical correlation between and for metal-oxychlorides was updated with the inclusion of the present data. According to the predicted (DbOCl), a (DbOCl) value of 135 2 kJ/mol was extrapolated. The future accomplishment of comparative studies with DbOCl under the same experimental conditions will provide valuable information on the volatility trend in Group-5 elements, together with an indication on the magnitude of relativistic effects on the electronic structure of dubnium.

First ionization potentials of Fm, Md, No, and Lr; Verification of filling-up of 5f electrons and confirmation of the actinide series

Sato, Tetsuya; Asai, Masato; Borschevsky, A.*; Beerwerth, R.*; Kaneya, Yusuke*; Makii, Hiroyuki; Mitsukai, Akina*; Nagame, Yuichiro; Osa, Akihiko; Toyoshima, Atsushi; et al.

Journal of the American Chemical Society, 140(44), p.14609 - 14613, 2018/11

https://doi.org/10.1021/jacs.8b09068

The first ionization potential (IP) yields information on valence electronic structure of an atom. IP values of heavy actinides beyond einsteinium (Es, Z = 99), however, have not been determined experimentally so far due to the difficulty in obtaining these elements on scales of more than one atom at a time. Recently, we successfully measured IP of lawrencium (Lr, Z = 103) using a surface ionization method. The result suggests that Lr has a loosely-bound electron in the outermost orbital. In contrast to Lr, nobelium (No, Z = 102) is expected to have the highest IP among the actinide elements owing to its full-filled 5f and the 7s orbitals. In the present study, we have successfully determined IP values of No as well as fermium (Fm, Z = 100) and mendelevium (Md, Z = 101) using the surface ionization method. The obtained results indicate that the IP value of heavy actinoids would increase monotonically with filling electrons up in the 5f orbital like heavy lanthanoids.

Extraction behavior of Mo and W from HSO and HF/HCl solutions into toluene with Aliquat336; Sulfate and fluoride complex formation of Mo and W towards chemical studies of seaborgium (Sg)

Toyoshima, Atsushi; Mitsukai, Akina; Tsukada, Kazuaki; Oe, Kazuhiro*; Haba, Hiromitsu*; Komori, Yukiko*; Murakami, Masashi; Kaneya, Yusuke*; Sato, Daisuke*; Asai, Masato; et al.

Journal of Radioanalytical and Nuclear Chemistry, 317(1), p.421 - 430, 2018/07

https://doi.org/10.1007/s10967-018-5882-5

We have studied extraction behavior of group-6 elements Mo and W to search for suitable conditions for an on-line extraction experiment of their heavier homolog, seaborgium (Sg). Batch-wise extraction of carrier-free radiotracers Mo and W were carried out from 0.10 - 8.6 M HSO and 1.010 - 5.0 M HF/1.0 M HCl into toluene with a quaternary ammonium compound, Aliquat336. Anionic sulfate complexes of Mo and W with charge - 2 were extracted with Aliquat336 from HSO solutions with concentrations of [HSO] 2 M. In HF/1.0 M HCl, oxyfluoro complexes of Mo and W with charge - 1 were interpreted to be formed and extracted with Aliquat336. From these results, favorable conditions for the extraction of Sg are discussed.