The investigation of the chemical properties of Superheavy Elements (SHEs) can only be performed by conducting experiments at the challenging “one-atom-at-a-time” level. The typical low production rates and short half-lives of SHEs strongly demands for rapid and efficient chemical setups. Nowadays, gas-chromatographic techniques (i.e., isothermal chromatography and thermochromatography) are the most suitable methods for studying such exotic nuclides. Comparative studies with SHEs and the corresponding lighter homologues in the very same chemical system are crucial for obtaining information on the volatility trend in a group. Since the conduction of the first SHEs gas-phase experiments in 1966, oxychloride species of rutherfordium (Rf, Z = 104), dubnium (Db, Z = 105), seaborgium (Sg, Z = 106), and bohrium (Bh, Z = 107) were observed. In the case of SgO2Cl2 and BhO3Cl, dedicated experiments aiming to their chemical exploration were conducted. Instead, the synthesis of RfOCl2 and DbOCl3 was obtained as a collateral effect due to O2 and water impurities in the gas-phase. Only recently, a systematic study on the chemical interaction of DbOCl3 and its lighter homologues NbOCl3 and TaOCl3 with quartz surfaces was performed. Based on the periodic trends along group 5 elements, an increased stability (and thus, a decreased volatility) for DbOCl3 in comparison to Nb and Ta was expected. However, preliminary results showed a NbOCl3 &gt; TaOCl3 ≥ DbOCl3 volatility sequence. The high volatility of DbOCl3 is perhaps due to strong relativistic effects in the Db electronic structure. A similar behavior cannot be excluded for the oxychlorides of group 4 elements. Thus, an experimental campaign dedicated to the study of ZrOCl2, HfOCl2, and RfOCl2 at the same chemical conditions is worth performing. As for Sg and Bh, the very limited number of observed events in former studies comports a 15% chance that SgO2Cl2 and BhO3Cl are equally or more volatile than their lighter homologues. Additional data are needed in order to come to statements with more statistical significance. Finally, oxychlorides might represent a key for conducting first gas-phase experiments with up-to-now unexplored elements, e.g., meitnerium (Mt, Z = 109), moscovium (Mc, Z = 115), and livermorium (Lv, Z = 116). Here, the latest results on gas-phase experiments with SHEs oxychlorides and future applications of this technique will be presented.

Revival of gas-phase chemistry with oxychlorides of superheavy elements

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.