A. Toyoshima

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.

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.

Adsorption of Db and its homologues Nb and Ta, and the pseudo-homologue Pa on anion-exchange resin in HF solution

Abstract Anion-exchange chromatography of element 105, dubnium (Db), produced in the 248Cm( 19F, 5n) 262Db reaction is investigated together with the homologues Nb and Ta, and the pseudo-homologue Pa in 13.9 M hydrofluoric acid (HF) solution. The distribution coefficient (Kd) of Db on an anion-exchange resin is successfully determined by running cycles of 1702 chromatographic column separations. The result clearly indicates that the adsorption of Db on the resin is significantly different from that of the homologues and that the adsorption of anionic fluoro complexes of these elements decreases in the sequence of Ta≈ Nb>Db≥Pa.

First successful ionization of Lr (Z = 103) by a surface-ionization technique

We have developed a surface ionization ion-source as part of the JAEA-ISOL (Isotope Separator On-Line) setup, which is coupled to a He/CdI2 gas-jet transport system to determine the first ionization potential of the heaviest actinide lawrencium (Lr, Z = 103). The new ion-source is an improved version of the previous source that provided good ionization efficiencies for lanthanides. An additional filament was newly installed to give better control over its operation. We report, here, on the development of the new gas-jet coupled surface ion-source and on the first successful ionization and mass separation of 27-s (256)Lr produced in the (249)Cf + (11)B reaction.

Decomposition studies of group 6 hexacarbonyl complexes. Part 1: Production and decomposition of Mo(CO)6 and W(CO)6

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.

Oxidation of Element 102, Nobelium, with Flow Electrolytic Column Chromatography on an Atom-at-a-Time Scale

We report here on the successful oxidation of element 102, nobelium (No), on an atom-at-a-time scale in 0.1 M alpha-hydroxyisobutyric acid (alpha-HIB) solution using a newly developed technique, flow electrolytic column chromatography. It is found that the most stable ion, No(2+), is oxidized to No(3+) within 3 min and that the oxidized No complex with alpha-HIB holds the trivalent state in the column above an applied potential of 1.0 V.

Ground-state band of the neutron-rich transuranium nucleus 250Cm154

The ground-state band of the neutron-rich transuranium nucleus 250 Cm was established up to spin 12 by in-beam γ-ray spectroscopy using the two-neutron transfer reaction with a 248 Cm target and a 162 MeV 18 O beam. Deexcitation γ rays in 250 Cm were identified by selecting the kinetic energies of 16 O particles using Si Δ E – E detectors. The moment of inertia of 250 Cm 154 is considerably smaller than that of 248 Cm 152 , which supports the existence of the deformed subshell closure at N =152 in Cm isotopes.

Sulfate complexation of element 104, Rf, in H2SO4/HNO3 mixed solution

Abstract The cation-exchange behavior of 261Rf (T1/2= 78 s) produced in the 248Cm(18O, 5n) reaction was studied on a “one-atom-at-a-time” scale in 0.15–0.69 M H2SO4/HNO3 mixed solutions ([H+]=1.0 M) using an automated ion-exchange separation apparatus coupled with the detection system for alpha-spectroscopy (AIDA). It was found that adsorption probabilities ( decrease with an increase of [HSO4−], showing a successive formation of Rf sulfate complexes. Rf exhibits a weaker complex formation tendency compared to the lighter homologues Zr and Hf. This is in good agreement with theoretical predictions including relativistic effects.

In-beam γ-ray study of the neutron-rich nuclei 240U, 246Pu, and 250Cm produced by the (18O, 16O) reaction

We have measured deexcitation γ rays in the neutron-rich nuclei of 240U, 246Pu, and 250Cm produced by the (18O, 16O) two-neutron transfer reactions, in coincidence with the 16O particles using Si ΔE−E detectors. The γ rays in these nuclei were identified by selecting the kinetic energies of 16O particles, which correspond to the excitation energies in the residual nuclei below the neutron separation energies. The ground-state bands of 240U, 246Pu, and 250Cm were established up to 12+ states and the Kπ = 0− octupole band of 240U was established up to 9− states. The systematics of the moments of inertia of the ground-state bands for actinide nuclei shows that the deformed subshell closure at N = 152 is sustained for 96Cm isotopes and that it disappears for 94Pu isotopes.

Measurement of the Md3+/Md2+ Reduction Potential Studied with Flow Electrolytic Chromatography

The reduction behavior of mendelevium (Md) was studied using a flow electrolytic chromatography apparatus. By application of the appropriate potentials on the chromatography column, the more stable Md(3+) is reduced to Md(2+). The reduction potential of the Md(3+) + e(-) → Md(2+) couple was determined to be -0.16 ± 0.05 V versus a normal hydrogen electrode.