Ch. E. Düllmann

Chemical investigation of hassium (element 108).

The periodic table provides a classification of the chemical properties of the elements. But for the heaviest elements, the transactinides, this role of the periodic table reaches its limits because increasingly strong relativistic effects on the valence electron shells can induce deviations from known trends in chemical properties. In the case of the first two transactinides, elements 104 and 105, relativistic effects do indeed influence their chemical properties, whereas elements 106 and 107 both behave as expected from their position within the periodic table. Here we report the chemical separation and characterization of only seven detected atoms of element 108 (hassium, Hs), which were generated as isotopes 269Hs (refs 8, 9) and 270Hs (ref. 10) in the fusion reaction between 26Mg and 248Cm. The hassium atoms are immediately oxidized to a highly volatile oxide, presumably HsO4, for which we determine an enthalpy of adsorption on our detector surface that is comparable to the adsorption enthalpy determined under identical conditions for the osmium oxide OsO4. These results provide evidence that the chemical properties of hassium and its lighter homologue osmium are similar, thus confirming that hassium exhibits properties as expected from its position in group 8 of the periodic table.

Direct Mapping of Nuclear Shell Effects in the Heaviest Elements

Pinning Down Nuclear Shells The nuclei of heavy atoms are destabilized by proton repulsions, and, conversely, the quantum-mechanical shell effects help to stabilize them. There are theoretical models for predicting the masses of yet-to-be-discovered superheavy elements, based on such shell effects, and these models can be tested by studying the shells of known actinide nuclei. The problem is that current mass values determined from studying radioactive decay products have substantial errors. Minaya Ramirez et al. (p. 1207, published online 9 August; see the Perspective by Bollen) were able to collect a sufficient number of nuclei of lawrencium and nobelium isotopes in an ion trap to determine their masses directly by mass spectroscopy. These results will be helpful in predicting the heaviest possible element. Highly precise mass measurements of nobelium and lawrencium isotopes provide insight into superheavy element stability. Quantum-mechanical shell effects are expected to strongly enhance nuclear binding on an “island of stability” of superheavy elements. The predicted center at proton number Z = 114, 120, or 126 and neutron number N = 184 has been substantiated by the recent synthesis of new elements up to Z = 118. However, the location of the center and the extension of the island of stability remain vague. High-precision mass spectrometry allows the direct measurement of nuclear binding energies and thus the determination of the strength of shell effects. Here, we present such measurements for nobelium and lawrencium isotopes, which also pin down the deformed shell gap at N = 152.

Thermochromatographic studies of mercury and radon on transition metal surfaces

Abstract In preparation for the experimental investigation of chemical properties of element 112 model studies were conducted based on the assumed similarity of element 112 to either the noble gas Rn or the transition metal Hg, its supposed lighter homologue in group 12. The adsorption behavior of elemental Hg on the transition metals Ag, Au, Ni, Pd, and Pt were investigated experimentally by off-line gas thermochromatography. The deduced adsorption data of Hg were compared with new values calculated using the Eichler–Miedema model. The observed sequence of increasing Hg-metal-interactions for Ag < Ni < Au < Pd < Pt confirms the predicted trend. The only exception was Pd, on which Hg was calculated to adsorb at a higher temperature than on Pt. Difficulties to obtain reproducible clean surfaces of Ag, Ni, Pd, and Pt led to the choice of Au as the best metal surface suitable to adsorb Hg. For fast on-line gas thermochromatography studies on metallic surfaces a new set-up was developed based on the In-situ Volatilization and On-line detection technique (IVO). This set-up was tested in on-line thermochromatographic investigations with short-lived Hg isotopes and 219Rn, using Au or Pd as stationary surfaces. An overall efficiency of about 60% and a transportation time less than 25 s was determined for this newly designed IVO. A separation factor of more than 106 was estimated for non-volatile species.

Measurement of the first ionization potential of lawrencium, element 103

The chemical properties of an element are primarily governed by the configuration of electrons in the valence shell. Relativistic effects influence the electronic structure of heavy elements in the sixth row of the periodic table, and these effects increase dramatically in the seventh row—including the actinides—even affecting ground-state configurations. Atomic s and p1/2 orbitals are stabilized by relativistic effects, whereas p3/2, d and f orbitals are destabilized, so that ground-state configurations of heavy elements may differ from those of lighter elements in the same group. The first ionization potential (IP1) is a measure of the energy required to remove one valence electron from a neutral atom, and is an atomic property that reflects the outermost electronic configuration. Precise and accurate experimental determination of IP1 gives information on the binding energy of valence electrons, and also, therefore, on the degree of relativistic stabilization. However, such measurements are hampered by the difficulty in obtaining the heaviest elements on scales of more than one atom at a time. Here we report that the experimentally obtained IP1 of the heaviest actinide, lawrencium (Lr, atomic number 103), is electronvolts. The IP1 of Lr was measured with 256Lr (half-life 27 seconds) using an efficient surface ion-source and a radioisotope detection system coupled to a mass separator. The measured IP1 is in excellent agreement with the value of 4.963(15) electronvolts predicted here by state-of-the-art relativistic calculations. The present work provides a reliable benchmark for theoretical calculations and also opens the way for IP1 measurements of superheavy elements (that is, transactinides) on an atom-at-a-time scale.

IVO, a device for in situ Volatilization and On-line detection of products from heavy ion reactions

Abstract A new gaschromatographic separation system to rapidly isolate heavy ion reaction products in the form of highly volatile species is described. Reaction products recoiling from the target are stopped in a gas volume and converted in situ to volatile species, which are swept by the carrier gas to a chromatography column. Species that are volatile under the given conditions pass through the column. In a cluster chamber, which is directly attached to the exit of the column, the isolated volatile species are chemically adsorbed to the surface of aerosol particles and transported to an on-line detection system. The whole set-up was tested using short-lived osmium (Os) and mercury (Hg) nuclides produced in heavy ion reactions to model future chemical studies with hassium (Hs, Z =108) and element 112. By varying the temperature of the isothermal section of the chromatography column between room temperature and −80°C, yield measurements of given species can be conducted, yielding information about the volatility of the investigated species.

Direct Measurement of the Mass Difference of

The atomic mass difference of (163)Ho and (163)Dy has been directly measured with the Penning-trap mass spectrometer SHIPTRAP applying the novel phase-imaging ion-cyclotron-resonance technique. Our measurement has solved the long-standing problem of large discrepancies in the Q value of the electron capture in (163)Ho determined by different techniques. Our measured mass difference shifts the current Q value of 2555(16) eV evaluated in the Atomic Mass Evaluation 2012 [G. Audi et al., Chin. Phys. C 36, 1157 (2012)] by more than 7σ to 2833(30(stat))(15(sys)) eV/c(2). With the new mass difference it will be possible, e.g., to reach in the first phase of the ECHo experiment a statistical sensitivity to the neutrino mass below 10 eV, which will reduce its present upper limit by more than an order of magnitude.

^{163}

Two short-lived isotopes ^{221}U and ^{222}U were produced as evaporation residues in the fusion reaction ^{50}Ti+^{176}Yb at the gas-filled recoil separator TASCA. An α decay with an energy of E_{α}=9.31(5)  MeV and half-life T_{1/2}=4.7(7)  μs was attributed to ^{222}U. The new isotope ^{221}U was identified in α-decay chains starting with E_{α}=9.71(5)  MeV and T_{1/2}=0.66(14)  μs leading to known daughters. Synthesis and detection of these unstable heavy nuclei and their descendants were achieved thanks to a fast data readout system. The evolution of the N=126 shell closure and its influence on the stability of uranium isotopes are discussed within the framework of α-decay reduced width.

Ho and

For measurements of the neutron-induced fission cross section of 242Pu, large-area (42cm2) 242Pu targets were prepared on Ti-coated Si wafers by means of constant current density molecular plating. Radiochemical separations were performed prior to the platings. Quantitative deposition yields (>95%) were determined for all targets by means of alpha-particle spectroscopy. Layer densities in the range of 100-150μg/cm2 were obtained. The homogeneity of the targets was studied by radiographic imaging. A comparative study between the quality of the layers produced on the Ti-coated Si wafers and the quality of layers grown on normal Ti foils was carried out by applying scanning electron microscopy and energy dispersive X-ray spectroscopy. Ti-coated Si wafers resulted clearly superior to Ti foils in the production of homogeneous 242Pu layers with minimum defectivity.

^{163}

At GSI Darmstadt, the gas-filled recoil separator transactinide separator and chemistry apparatus (TASCA) is in operation for experiments with superheavy elements. It is optimized for hot-fusion reactions with actinide targets. The small cross sections of such reactions require the capability to accept highest beam intensities. The limited availability of some of the exotic actinide isotopes limits the size of target systems. To maintain target integrity during long experiments, automated target monitoring and control is necessary. Here, the TASCA target wheel system and the on-line target monitoring are described.

Dy Solves the

Abstract Chemical studies of superheavy elements require fast and efficient techniques, due to short half-lives and low production rates of the investigated nuclides. Here, we advocate for using a tubular flow reactor for assessing the thermal stability of the Sg carbonyl complex – Sg(CO)6. The experimental setup was tested with Mo and W carbonyl complexes, as their properties are established and supported by theoretical predictions. The suggested approach proved to be effective in discriminating between the thermal stabilities of Mo(CO)6 and W(CO)6. Therefore, an experimental verification of the predicted Sg–CO bond dissociation energy seems to be feasible by applying this technique. By investigating the effect of 104,105Mo beta-decay on the formation of 104,105Tc carbonyl complex, we estimated the lower reaction time limit for the metal carbonyl synthesis in the gas phase to be more than 100 ms. We examined further the influence of the wall material of the recoil chamber, the carrier gas composition, the gas flow rate, and the pressure on the production yield of 104Mo(CO)6, so that the future stability tests with Sg(CO)6 can be optimized accordingly.