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. 14…

Chemical studies of Fl (element 114): Heaviest chemically studied element

Extraction behavior of rutherfordium into tributylphosphate from hydrochloric acid

The extraction behavior of rutherfordium (Rf) into tributylphosphate (TBP) from hydrochloric acid (HCl) has been studied together with those of the lighter group-4 elements Zr and Hf. The extractability of261Rf,169Hf, and85Zr into TBP was investigated under identical conditions in 7.2–8.0 M HCl by on-line reversed-phase extraction chromatography. The percent extractions of Rf, Hf, and Zr into the TBP resin increase steeply with increasing HCl concentration, and the order of extraction is Zr > Hf ≈ Rf. By considering the order of chloride complexation among these elements, it is suggested that the stability of the TBP complex of Rf tetrachloride is lower than those of Zr and Hf.

Measurement of Evaporation Residue and Fission Cross Sections of the Reaction 30Si + 238U at Subbarrier Energies

Effects of the prolate deformation of 238 U on fusion were studied in the reaction 30 Si + 238 U at bombarding energies close to the Coulomb barrier. The fission (capture) cross sections were measured at the JAEA tandem accelerator to see the enhancement of the cross sections in the subbarrier energy due to the lower Coulomb barrier in the collisions of projectile at the polar sides of 238 U. In order to obtain the direct evidence for complete fusion, evaporation residue cross sections were measured at UNILAC of GSI. At the subbarrier energy of Ec.m. = 133.0 MeV, where only polar collisions to 238 U occur, we measured three spontaneously fissioning nuclei which we assigned to the isotope 26…

Fluoride Complexation of Element 104, Rutherfordium (Rf), Investigated by Cation-exchange Chromatography

We report on new and much more precise cation-exchange data of element 104, rutherfordium (Rf), in the fluoride ion concentration [F−] range of 5.29×10−5−1.04×10−3 M. The result based on one-atom-a...

First ionization potential of the heaviest actinide lawrencium, element 103

The first ionization potential (IP1 ) of element 103, lawrencium (Lr), has been successfully determined for the first time by using a newly developed method based on a surface ionization process. The measured IP 1 value is 4.9630.08 0.07 eV. This value is the smallest among those of actinide elements and is in excellent agreement with the value of 4.963(15) eV predicted by state-of-the-art relativistic calculations also performed in this work. Our results strongly support that the Lr atom has an electronic configuration of [Rn]7s 2 5f 14 7p 1 1/2 , which is influenced by strong relativistic effects. The present work provides a reliable benchmark for theoretical calculations and also opens t…

Complex chemistry with complex compounds

In recent years gas-phase chemical studies assisted by physical pre-separation allowed for the investigation of fragile single molecular species by gas-phase chromatography. The latest success with the heaviest group 6 transactinide seaborgium is highlighted. The formation of a very volatile hexacarbonyl compound Sg(CO)6 was observed similarly to its lighter homologues molybdenum and tungsten. The interactions of these gaseous carbonyl complex compounds with quartz surfaces were investigated by thermochromatography. Second-generation experiments are under way to investigate the intramolecular bond between the central metal atom of the complexes and the ligands addressing the influence of re…

First Ionization Potentials of Fm, Md, No, and Lr

We report the first ionization potentials (IP1) of the heavy actinides, fermium (Fm, atomic number Z = 100), mendelevium (Md, Z = 101), nobelium (No, Z = 102), and lawrencium (Lr, Z = 103), determined using a method based on a surface ionization process coupled to an online mass separation technique in an atom-at-a-time regime. The measured IP1 values agree well with those predicted by state-of-the-art relativistic calculations performed alongside the present measurements. Similar to the well-established behavior for the lanthanides, the IP1 values of the heavy actinides up to No increase with filling up the 5f orbital, while that of Lr is the lowest among the actinides. These results clear…

Anionic Fluoro Complex of Element 105, Db

We report on the characteristic anion-exchange behavior of the superheavy element dubnium (Db) with atomic number Z=105 in HF/HNO3 solution at the fluoride ion concentration [F−]=0.003 M. The resul...

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 in…

Chemical studies on rutherfordium (Rf) at JAERI

SummaryChemical studies on element 104, rutherfordium (Rf), at JAERI (Japan Atomic Energy Research Institute) are reviewed. The transactinide nuclide261Rf has been produced in the reaction248Cm(18O, 5n) at the JAERI tandem accelerator with the production cross section of about 13 nb. On-line anion-exchange experiments on Rf together with the lighter homologues, group-4 elements Zr and Hf, in acidic solutions have been conducted with a rapid ion-exchange separation apparatus. From the systematic study of the anion-exchange behavior of Rf, it has been found that the properties of Rf in HCl and HNO3solutions are quite similar to those of Zr and Hf, definitely confirming that Rf is a member of …

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.

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.

Measurement of the first ionization potential of lawrencium (element 103)

Lawrencium, with atomic number 103, has an isotope with a half-life of 27 seconds; even so, its first ionization potential has now been measured on an atom-at-a-time scale and agrees well with state-of-the-art theoretical calculations that include relativistic effects. The most dramatic modern revision of Mendeleev's periodic table of elements came in 1944 when Glenn T. Seaborg placed a new series of elements, the actinides (atomic numbers 89–103), below the lanthanides. In this issue of Nature, Yuichiro Nagame and colleagues report the first measurement of one of the basic atomic properties of element 103 (lawrencium), namely its first ionization potential. Lawrencium is only accessible vi…

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

Anion-exchange chromatography of element 105, dubnim (Db), produced in the 206 Cm( 19 F, 5n) 262 Db 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 (K d ) 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.

Fluoride Complexation of Element 104, Rutherfordium

Fluoride complexation of element 104, rutherfordium (Rf), produced in the 248Cm(18O,5n)261Rf reaction has been studied by anion-exchange chromatography on an atom-at-a-time scale. The anion-exchange chromatographic behavior of Rf was investigated in 1.9-13.9 M hydrofluoric acid together with those of the group-4 elements Zr and Hf produced in the 18O-induced reactions on Ge and Gd targets, respectively. It was found that the adsorption behavior of Rf on anion-exchange resin is quite different from those of Zr and Hf, suggesting the influence of relativistic effects on the fluoride complexation of Rf.

Hexafluoro complex of rutherfordium in mixed HF/HNO3 solutions

Formation of anionic fluoride-complexes of element 104, rutherfordium, produced in the 248 Cm( 18 O, 5n) 261 Rf reaction was studied by anion-exchange on an atom-at-a-time scale. It was found that the hexafluoro complex of Rf, [RfF 6 ] 2- , was formed in the studied fluoride ion concentrations of 0.0005-0.013 M. Formation of [RfF 6 ] 2- was significantly different from that of the homologues Zr and Hf, [ZrF 6 ] 2- and [HfF 6 ] 2- ; the evaluated formation constant of [RfF 6 ] 2- is at least one-order of magnitude smaller than those of [ZrF 6 ] 2- and [HfF 6 ] 2- .

Fluorido Complex Formation of Element 104, Rutherfordium (Rf)

We have investigated the cation-exchange behavior of element 104, rutherfordium (Rf), together with its lighter group-4 homologs Zr and Hf, and the tetravalent pseudo-homolog Th in HF/HNO3 mixed so...

First online operation of TRIGA-TRAP

Abstract We report on the successful coupling of the Penning-trap mass spectrometry setup TRIGA-TRAP to the research reactor TRIGA Mainz. This offers the possibility to perform direct high-precision mass measurements of short-lived nuclei produced in neutron-induced fission of a 235 U target located near the reactor core. An aerosol-based gas-jet system is used for efficient transport of short-lived neutron-rich nuclei from the target chamber to a surface ion source. In conjunction with new ion optics and extended beam monitoring capabilities, the experimental setup has been fully commissioned. The design of the surface ion source, efficiency studies and first results are presented.

Extraction Chromatographic Behavior of Rf, Zr, and Hf in HCl Solution with Styrenedivinylbenzene Copolymer Resin Modified by TOPO (trioctylphosphine oxide)

It is of great interest to study chemical properties of the transactinide elements with atomic numbers (Z) ≥ 104. One of the most important subjects is to establish the position of the elements at the extreme end of the periodic table. To this end we perform studies of chemical properties of these transactinides and compare them with those of their lighter homologues and with the ones expected from extrapolations in the periodic table. So far, chromatographic studies of the transactinides have provided experimental proof of placing rutherfordium (Rf, Z = 104) through hassium (Hs, Z = 108) into groups 4 to 8, respectively. 1-10 Quite recently, copernicium (Cn, Z = 112) has been shown to be a…

TASCAを用いたCn, Nh, Fl化学実験のためのHg, Tl, PbのSiO2及びAu表面に対するオンライン化学吸着研究

Online gas-solid adsorption studies with single atom quantities of Hg, Tl, and Pb on SiO$_{2}$ and Au surfaces were carried out using short-lived radioisotopes with half-lives in the range of 4-49 s. This is a model study to measure adsorption enthalpies of superheavy elements Cn, Nh, and Fl. The short-lived isotopes were produced and separated by the gas-filled recoil separator TASCA at GSI. The products were stopped in He gas, and flushed into gas chromatography columns made of Si detectors whose surfaces were covered by SiO$_{2}$ or Au. The short-lived Tl and Pb were successfully measured by the Si detectors with the SiO$_{2}$ surface at room temperature. On the other hand, the Hg did no…