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.

Charge radii and electromagnetic moments of At

Cubiss, J.*; Andreyev, A. N.; Mitsuoka, Shinichi*; Nagame, Yuichiro; Nishio, Katsuhisa; Ota, Shuya*; Wakabayashi, Yasuo*; 60 of others*

Physical Review C, 97(5), p.054327_1 - 054327_19, 2018/05

https://doi.org/10.1103/PhysRevC.97.054327

Chemical properties of rutherfordium (Rf) and dubnium (Db) in the aqueous phase

Nagame, Yuichiro; Kratz, J. V.*; Schdel, M.*

EPJ Web of Conferences, 131, p.07007_1 - 07007_8, 2016/12

BB2016-0022.pdf:0.96MB

https://doi.org/10.1051/epjconf/201613107007

Complex chemistry with complex compounds

Eichler, R.*; Asai, Masato; Brand, H.*; Chiera, N. M.*; Di Nitto, A.*; Dressler, R.*; Dllmann, Ch. E.*; Even, J.*; Fangli, F.*; Goetz, M.*; et al.

EPJ Web of Conferences, 131, p.07005_1 - 07005_7, 2016/12

https://doi.org/10.1051/epjconf/201613107005

In recent years gas-phase chemical studies assisted by physical pre-separation allowed for the productions and investigations of fragile single molecular species of superheavy elements. The latest highlight is the formation of very volatile hexacarbonyl compound of element 106, Sg(CO). Following this success, second-generation experiments were performed to measure the first bond dissociation energy between the central metal atom and the surrounding ligand. The method using a tubular decomposition reactor was developed and successfully applied to short-lived Mo(CO), W(CO), and Sg(CO).

Vacuum chromatography of Tl on SiO at the single-atom level

Steinegger, P.*; Asai, Masato; Dressler, R.*; Eichler, R.*; Kaneya, Yusuke*; Mitsukai, Akina*; Nagame, Yuichiro; Piguet, D.*; Sato, Tetsuya; Schdel, M.; et al.

Journal of Physical Chemistry C, 120(13), p.7122 - 7132, 2016/04

https://doi.org/10.1021/acs.jpcc.5b12033

A new experimental method "vacuum chromatography" has been developed to measure adsorption enthalpy of superheavy elements, and its feasibility has been examined using short-lived thallium isotopes. The short-lived thallium isotopes were produced at the JAEA tandem accelerator. The thallium ion beam prepared with an on-line isotope separator which ionized and mass-separated the thallium isotopes was injected into an isothermal vacuum chromatography apparatus. A temperature-dependent adsorption property of thallium atom on SiO surface were measured. The adsorption enthalpy of thallium was determined to be 158 kJ/mol. The thallium is a homolog of element 113. Thus, the vacuum chromatography developed in this study enables us to perform chemical experiments for short-lived superheavy elements with half-lives of a order of one second.