Christoph E. Düllmann

Superheavy Element Flerovium (Element 114) Is a Volatile Metal

The electron shell structure of superheavy elements, i.e., elements with atomic number Z ≥ 104, is influenced by strong relativistic effects caused by the high Z. Early atomic calculations on element 112 (copernicium, Cn) and element 114 (flerovium, Fl) having closed and quasi-closed electron shell configurations of 6d(10)7s(2) and 6d(10)7s(2)7p1/2(2), respectively, predicted them to be noble-gas-like due to very strong relativistic effects on the 7s and 7p1/2 valence orbitals. Recent fully relativistic calculations studying Cn and Fl in different environments suggest them to be less reactive compared to their lighter homologues in the groups, but still exhibiting a metallic character. Experimental gas-solid chromatography studies on Cn have, indeed, revealed a metal-metal bond formation with Au. In contrast to this, for Fl, the formation of a weak bond upon physisorption on a Au surface was inferred from first experiments. Here, we report on a gas-solid chromatography study of the adsorption of Fl on a Au surface. Fl was produced in the nuclear fusion reaction (244)Pu((48)Ca, 3-4n)(288,289)Fl and was isolated in-flight from the primary (48)Ca beam in a physical recoil separator. The adsorption behavior of Fl, its nuclear α-decay product Cn, their lighter homologues in groups 14 and 12, i.e., Pb and Hg, and the noble gas Rn were studied simultaneously by isothermal gas chromatography and thermochromatography. Two Fl atoms were detected. They adsorbed on a Au surface at room temperature in the first, isothermal part, but not as readily as Pb and Hg. The observed adsorption behavior of Fl points to a higher inertness compared to its nearest homologue in the group, Pb. However, the measured lower limit for the adsorption enthalpy of Fl on a Au surface points to the formation of a metal-metal bond of Fl with Au. Fl is the least reactive element in the group, but still a metal.

Direct detection of the 229Th nuclear clock transition

Today’s most precise time and frequency measurements are performed with optical atomic clocks. However, it has been proposed that they could potentially be outperformed by a nuclear clock, which employs a nuclear transition instead of an atomic shell transition. There is only one known nuclear state that could serve as a nuclear clock using currently available technology, namely, the isomeric first excited state of 229Th (denoted 229mTh). Here we report the direct detection of this nuclear state, which is further confirmation of the existence of the isomer and lays the foundation for precise studies of its decay parameters. On the basis of this direct detection, the isomeric energy is constrained to between 6.3 and 18.3 electronvolts, and the half-life is found to be longer than 60 seconds for 229mTh2+. More precise determinations appear to be within reach, and would pave the way to the development of a nuclear frequency standard.

Direct detection of the Th-229 nuclear clock transition

Today’s most precise time and frequency measurements are performed with optical atomic clocks. However, it has been proposed that they could potentially be outperformed by a nuclear clock, which employs a nuclear transition instead of an atomic shell transition. There is only one known nuclear state that could serve as a nuclear clock using currently available technology, namely, the isomeric first excited state of 229Th (denoted 229mTh). Here we report the direct detection of this nuclear state, which is further confirmation of the existence of the isomer and lays the foundation for precise studies of its decay parameters. On the basis of this direct detection, the isomeric energy is constrained to between 6.3 and 18.3 electronvolts, and the half-life is found to be longer than 60 seconds for 229mTh2+. More precise determinations appear to be within reach, and would pave the way to the development of a nuclear frequency standard.

Synthesis and detection of a seaborgium carbonyl complex

A carbonyl compound that tips the scales Life is short for the heaviest elements. They emerge from high-energy nuclear collisions with scant time for detection before they break up into lighter atoms. Even et al. report that even a few seconds is long enough for carbon to bond to the 106th element, seaborgium (see the Perspective by Loveland). The authors used a custom apparatus to direct the freshly made atoms out of the hot collision environment and through a stream of carbon monoxide and helium. They compared the detected products with theoretical modeling results and conclude that hexacarbonyl Sg(CO)6 was the most likely structural formula. Science, this issue p. 1491; see also p. 1451 A special apparatus enables synthesis of a compound with carbon bonds to a short-lived element produced via nuclear reaction. [Also see Perspective by Loveland] Experimental investigations of transactinoide elements provide benchmark results for chemical theory and probe the predictive power of trends in the periodic table. So far, in gas-phase chemical reactions, simple inorganic compounds with the transactinoide in its highest oxidation state have been synthesized. Single-atom production rates, short half-lives, and harsh experimental conditions limited the number of experimentally accessible compounds. We applied a gas-phase carbonylation technique previously tested on short-lived molybdenum (Mo) and tungsten (W) isotopes to the preparation of a carbonyl complex of seaborgium, the 106th element. The volatile seaborgium complex showed the same volatility and reactivity with a silicon dioxide surface as those of the hexacarbonyl complexes of the lighter homologs Mo and W. Comparison of the product’s adsorption enthalpy with theoretical predictions and data for the lighter congeners supported a Sg(CO)6 formulation.

Atom-at-a-time laser resonance ionization spectroscopy of nobelium

Optical spectroscopy of a primordial isotope has traditionally formed the basis for understanding the atomic structure of an element. Such studies have been conducted for most elements and theoretical modelling can be performed to high precision, taking into account relativistic effects that scale approximately as the square of the atomic number. However, for the transfermium elements (those with atomic numbers greater than 100), the atomic structure is experimentally unknown. These radioactive elements are produced in nuclear fusion reactions at rates of only a few atoms per second at most and must be studied immediately following their production, which has so far precluded their optical spectroscopy. Here we report laser resonance ionization spectroscopy of nobelium (No; atomic number 102) in single-atom-at-a-time quantities, in which we identify the ground-state transition 1S0 1P1. By combining this result with data from an observed Rydberg series, we obtain an upper limit for the ionization potential of nobelium. These accurate results from direct laser excitations of outer-shell electrons cannot be achieved using state-of-the-art relativistic many-body calculations that include quantum electrodynamic effects, owing to large uncertainties in the modelled transition energies of the complex systems under consideration. Our work opens the door to high-precision measurements of various atomic and nuclear properties of elements heavier than nobelium, and motivates future theoretical work.

Rapid synthesis of radioactive transition-metal carbonyl complexes at ambient conditions.

Carbonyl complexes of radioactive transition metals can be easily synthesized with high yields by stopping nuclear fission or fusion products in a gas volume containing CO. Here, we focus on Mo, W, and Os complexes. The reaction takes place at pressures of around 1 bar at room temperature, i.e., at conditions that are easy to accommodate. The formed complexes are highly volatile. They can thus be transported within a gas stream without major losses to setups for their further investigation or direct use. The rapid synthesis holds promise for radiochemical purposes and will be useful for studying, e.g., chemical properties of superheavy elements.

Extraction of short-lived zirconium and hafnium isotopes using crown ethers: A model system for the study of rutherfordium

Summary The extraction of zirconium and hafnium from hydrochloric acid media was studied using the crown ethers dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6 (DC18C6) and dicyclohexano-24-crown-8 (DC24C8) as extractants. The goal was to find an extraction system that exhibits a high selectivity between the members of group 4 of the periodic table and is suitable for the study of rutherfordium. It was found that Zr and Hf are both extracted using DB18C6, DC18C6 and DC24C8. The extraction yield increases with increasing acid concentration and increasing concentration of crown ether. The extracted species most likely consists of an ion-association complex formed between a Zr or Hf chloro complex and a hydronium crown ether complex. Conditions can be found for each extractant that provide for the separation of Zr from Hf. This selective separation between Zr and Hf makes the extraction with crown ethers from HCl well suited to study the extraction behaviour of Rf and compare it to the behaviour of Zr and Hf. These extraction systems can be used to determine whether the extraction behaviour of Rf is similar to Zr, similar to Hf or follows the trend established by the lighter homologs. The extraction kinetics are fast enough for the study of the 78-s isotope 261mRf.

In-situ formation, thermal decomposition, and adsorption studies of transition metal carbonyl complexes with short-lived radioisotopes

Abstract We report on the in-situ synthesis of metal carbonyl complexes with short-lived isotopes of transition metals. Complexes of molybdenum, technetium, ruthenium and rhodium were synthesized by thermalisation of products of neutron-induced fission of 249Cf in a carbon monoxide-nitrogen mixture. Complexes of tungsten, rhenium, osmium, and iridium were synthesized by thermalizing short-lived isotopes produced in 24Mg-induced fusion evaporation reactions in a carbon monoxide containing atmosphere. The chemical reactions took place at ambient temperature and pressure conditions. The complexes were rapidly transported in a gas stream to collection setups or gas phase chromatography devices. The physisorption of the complexes on Au and SiO2 surfaces was studied. We also studied the stability of some of the complexes, showing that these start to decompose at temperatures above 300 ℃ in contact with a quartz surface. Our studies lay a basis for the investigation of such complexes with transactinides.

Superheavy element studies with preseparated isotopes

Abstract In recent years, significant progress in the field of superheavy element research has been achieved thanks to a novel combination of techniques from different fields. This “physical preseparation” approach includes the coupling of an ancillary setup – typically a chemistry apparatus or a counting setup – to a physical recoil separator. This latter preseparator removes unwanted nuclear reaction products as well as the intense heavy-ion beam associated with superheavy element experiments and thus isolates the evaporation residues of the nuclear fusion reactions. These are guided to the separatorss focal plane, where they are extracted and available for further transport to external setups, e.g., by a gas-jet. In this overview, the development of physical preseparation is described, and experimental results from nuclear chemistry and physics that were achieved with “preseparated” isotopes are summarized, with an emphasis on results relevant for superheavy element research. The covered topics range from chemical studies in the liquid as well as in the gas phase, the measurement of nuclear decay properties and of atomic masses. Preseparation was already shown to be a very powerful approach in these studies and promises to allow further progress in superheavy element research.

Superheavy elements at GSI: a broad research program with element 114 in the focus of physics and chemistry

Abstract Studies of the superheavy elements form one of the pillars of the GSI research program. A unique combination of experimental facilities is installed at the GSI. Various topics, ranging from the synthesis of new elements, spectroscopy experiments to study the nuclear structures of the heaviest nuclei, highly accurate mass measurements beyond uranium, to chemical investigations of elements around element 114 and the synthesis of novel chemical superheavy element compound classes are being studied. This is complemented by fully relativistic quantum chemical calculations. As a recent highlight, the 244Pu(48Ca,3–4n)288,289114 reaction was studied, leading to the observation of element 114 at the new gas-filled recoil separator TASCA.