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Studies of the chemical properties of the elements at the uppermost end of the Periodic Table are extremely challenging both experimentally and theoretically. One of the most important and interesting subjects is to clarify the basic chemical properties of these elements as well as to elucidate the influence of relativistic effects on their electronic configuration. Isotopes of these elements produced at accelerators, however, are short-lived, and the number of produced atoms is so small; any chemistry to be performed must be done on an atom-at-a-time basis that imposes stringent limits on experimental procedures. Here we describe our recent achievements in the effective production of low-energy ion-beams of the elements at the end of the actinide series, fermium (Fm, atomic number Z = 100), mendelevium (Md, Z = 101), nobelium (No, Z = 102), and lawrencium (Lr, Z = 103), using a surface ionization ion-source installed in the ISOL (Isotope Separator On-Line) at the Tandem accelerator facility of JAEA (Japan Atomic Energy Agency). Then the successful measurements of the first ionization potentials (IP1) of these elements with the ISOL setup are reviewed. The measured IP1 values increased up to No via Fm and Md, while that of Lr was the lowest among the actinides. Based on the variation of the IP1 values of the heavy actinides with the atomic number in comparison with those of the heavy lanthanides, the results clearly demonstrated that the 5f orbitals are fully filled at No, and the actinide series ends with Lr. Furthermore, the IP1 value of Lr provoked controversy over its position in the Periodic Table, so a short introduction to this issue is presented. The feasibility of the extension of chemical studies to still heavier elements with their ion-beams generated by ISOL is briefly discussed. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Niobium. • Tantalum. • Dubnium. • Oxychlorides. • Adsorption enthalpy. Abstract The formation of NbOCl 3 and TaOCl 3 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 (Δ H ads) at zero surface coverage of –Δ H ads (NbOCl 3) = 102 ± 4 kJ/mol and –Δ H ads (TaOCl 3) = 128 ± 5 kJ/mol were determined by analyzing the chromatographic behavior of the Nb and Ta complexes with a Monte-Carlo simulation method based on an adsorption–desorption kinetic model. By applying an empirical correlation, the experimental Δ H ads values were successively related to the macroscopic standard sublimation enthalpy, Δ H° subl , 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 Δ H ads and Δ H° subl for metal-oxychlorides was updated with the inclusion of the present data. According to the predicted Δ H° subl (DbOCl 3), a Δ H ads (DbOCl 3) value of 135 ± 2 kJ/mol was extrapolated. The future accomplishment of comparative studies with DbOCl 3 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. [ABSTRACT FROM AUTHOR]