Toward volatile metal complexes of rutherfordium - results of testexeriments with Zr and Hf

The chemical investigation of the transactinide elements (TAN, Z {ge}104) is a topic of great interest in recent nuclear chemistry research. The highly charged nucleus accelerates the innermost electrons to relativistic velocities thus causing contraction of spherical (s, p{sub 1/2}) orbitals and expansion of the others (p{sub 3/2}, d, and f), which directly affects the chemical behavior of these elements. Deviations from trends established in the periodic table may therefore occur due to these so-called relativistic effects [1,2]. In gas phase experiments, mostly volatile inorganic compounds (e.g., halides or oxides) of TAN were investigated. We refer to [3] for a recent review. For reasons such as low production cross-sections or short half-lives, but also technical challenges, more sophisticated chemical studies have not yet been possible. One restriction in present TAN research is the plasma behind the target caused by the intense heavy ion beam. ''Weak'' molecules (e.g., organic ligands) are immediately destroyed, thus limiting the possibilities of synthesizing chemical compounds directly behind the target to ''simple'' and robust inorganic compounds. It is highly desirable to expand the knowledge on the chemical behavior of the TAN to other compound classes, e.g., volatile metal complexes. The use of the Berkeley Gas-filled Separator (BGS) [4] as a physical preseparator makes such studies possible by separating the beam from the desired TAN isotopes

Gas chemical investigation of hafnium and zirconium complexes with hexafluoroacetylacetone using preseparated short-lived radioisotopes

Volatile metal complexes of the group 4 elements Zr and Hf with hexafluoroacetylacetonate (hfa) have been studied using short-lived radioisotopes of the metals. The new technique of physical preseparation has been employed where reaction products from heavy-ion induced fusion reactions are isolated in a physical recoil separator - the Berkeley Gas-filled Separator in our work - and made available for chemistry experiments. Formation and decomposition of M(hfa)4 (M=Zr, Hf) has been observed and the interaction strength with a fluorinated ethylene propylene (FEP) Teflon surface has been studied. From the results of isothermal chromatography experiments, an adsorption enthalpy of -ΔHa=(57±3)kJ/mol was deduced. In optimization experiments, the time for formation of the complex and its transport to a counting setup installed outside of the irradiation cave was minimized and values of roughly one minute have been reached. The half-life of 165Hf, for which conflicting values appear in the literature, was measured to be (73.9±0.8)s. Provided that samples suitable for α-spectroscopy can be prepared, the investigation of rutherfordium (Rf), the transactinide member of group 4, appears possible. In the future, based on the studies presented here, it appears possible to investigate short-lived single atoms produced with low rates ( e.g. , transactinide isotopes) in completely new chemical systems, e.g. , as metal complexes with organic ligands as used here or as organometallic compound

The influence of projectile neutron number in the 208Pb(48Ti, n)255Rf and 208Pb(50Ti, n)257Rf reactions

Four isotopes of rutherfordium,254-257Rf, were produced by the 208Pb(48Ti, xn)256-xRf and 208Pb(50Ti, xn)258-xRf reactions (x = 1, 2) at the Lawrence Berkeley National Laboratory 88-Inch Cyclotron. Excitation functions were measured for the 1n and 2n exit channels. A maximum likelihood technique, which correctly accounts for the changing cross section at all energies subtended by the targets, was used to fit the 1n data to allow a more direct comparison between excitation functions obtained under different experimental conditions. The maximum 1n crosssections of the 208Pb(48Ti, n)255Rf and 208Pb(50Ti, n)257Rf reactions obtained from fits to the experimental data are 0.38 +/- 0.07 nb and 40 +/-5 nb, respectively. Excitation functions for the 2n exit channel were also measured, with maximum cross sections of nb for the 48Ti induced reaction, and 15.7 +/- 0.2 nb for the 50Ti induced reaction. The impact of the two neutron difference in the projectile on the 1n cross section is discussed. The results are compared to the Fusion by Diffusion model developed by Swiatecki, Wilczynska, and Wilczynski

Influence of projectile neutron number on cross section in cold fusion reactions

Elements 107-112 [1,2] have been discovered in reactions between {sup 208}Pb or {sup 209}Bi targets and projectiles ranging from {sup 54}Cr through {sup 70}Zn. In such reactions, the compound nucleus can be formed at excitation energies as low as {approx}12 MeV, thus this type of reaction has been referred to as 'cold fusion'. The study of cold fusion reactions is an indispensable approach to gaining a better understanding of heavy element formation and decay. A theoretical model that successfully predicts not only the magnitudes of cold fusion cross sections, but also the shapes of excitation functions and the cross section ratios between various reaction pairs was recently developed by Swiatecki, Siwek-Wilczynska, and Wilczynski [3,4]. This theoretical model, also referred to as Fusion by Diffusion, has been the guide in all of our cold fusion studies. One particularly interesting aspect of this model is the large predicted difference in cross sections between projectiles differing by two neutrons. The projectile pair where this difference is predicted to be largest is {sup 48}Ti and {sup 50}Ti. To test and extend this model, {sup 208}Pb({sup 48}Ti,n){sup 255}Rf and {sup 208}Pb({sup 50}Ti,n){sup 257}Rf excitation functions were recently measured at the Lawrence Berkeley National Laboratory's (LBNL) 88-Inch Cyclotron utilizing the Berkeley Gas-filled Separator (BGS). The {sup 50}Ti reaction was carried out with thin lead targets ({approx}100 {micro}g/cm{sup 2}), and the {sup 48}Ti reaction with both thin and thick targets ({approx}470 {micro}g/cm{sup 2}). In addition to this reaction pair, reactions with projectile pairs {sup 52}Cr and {sup 54}Cr [5], {sup 56}Fe and {sup 58}Fe [6], and {sup 62}Ni [7] and {sup 64}Ni [8] will be discussed and compared to the Fusion by Diffusion predictions. The model predictions show a very good agreement with the data

Entrance-channel effects in odd-Z tranactinide compound nucleus reactions

Swiatecki, Siwek-Wilczynska, and Wilczynski's 'Fusion By Diffusion' description [1] of transactinide (TAN) compound nucleus (CN) formation utilizes a three-step model. The first step is the 'sticking', or capture, which can be calculated relatively accurately. The second step is the probability for the formation of a CN by 'diffusion' analogous to that of Brownian motion. Lastly, there exists the probability of the CN 'surviving' deexcitation by neutron emission, which competes with fission and other de-excitation modes. This model predicts and reproduces cross sections typically within a factor of two. Producing the same CN with different projectile-target pairs is a very sensitive way to test entrance channel effects on heavy element production cross sections. If the same CN is produced at or near the same excitation energy the survival portion of the theory is nearly identical for the two reactions. This method can be used as a critical test of the novel 'diffusion' portion of the model. The reactions producing odd-Z TAN CN such as Db, Bh, Mt, and Rg (Z = 105, 107, 109, and 111, respectively) were first studied using even-Z projectiles on {sup 209}Bi targets (as opposed to odd-Z projectiles on {sup 208}Pb targets) because lower effective fissility [2] was expected to lead to larger cross sections. Many odd-Z projectile reactions producing odd-Z CN had not been studied in-depth until very recently. We have completed studies of these reaction pairs with the 88-Inch Cyclotron and the Berkeley Gas-Filled Separator (BGS) at the Lawrence Berkeley National Laboratory (LBNL), see Figure 1. Cross section ratios for several pairs of reactions will be presented and compared with theory

Extraction systems for the study of dubnium

The chemistry of transactinide elements (Z {ge} 104) is a topic of great interest in current nuclear chemistry research. The chemical systems that can be used in these studies are limited by the short half-lives of the isotopes and the small production rates of atoms per minute or even atoms per week. In the initial investigations, the chemistry used had to be very selective to the periodic group of interest to separate the transactinide atom from all the other unwanted nuclear reaction products, e.g., transfer products. By using the Berkeley Gas-filled Separator (BGS) as a physical pre-separator, we are able concentrate on systems that are selective between the members of the group of interest, because all other interfering products and the beam are being suppressed by the BGS [1]. We are developing suitable extraction systems for the study of element 105, dubnium. For this purpose we have studied the extraction of niobium and tantalum, the lighter homologs of dubnium, from mineral acids with different organophosphorus compounds. All studies were performed online, using short-lived niobium and tantalum produced in the {sup 124}Sn({sup 51}V,5n){sup 170}Ta and {sup 74}Se({sup 18}O,p3n){sup 88}Nb reactions. This allowed for the study of the lighter homologues at metal concentrations of 10{sup -16} M. At these low metal concentrations, the formation of polymeric species is largely prohibited. As seen in Fig. 1, by varying the extractant and the hydrochloric acid concentration from 1 to 11 M, we are able to see a difference in extraction behavior between niobium and tantalum. While the system is suitable for determining chemical differences between the lighter homologues, the extraction of tantalum from hydrochloric acid shows slow kinetics. Figure 2 shows that after 90 seconds of mixing, the system is not in equilibrium. However, experiments indicate that equilibrium is reached faster at higher acid concentrations. We have studied the influence of hydrogen ion concentration on the extraction kinetics. By varying the chloride concentration while holding the hydrogen ion concentration at a low, fixed value, equilibrium can be reached in less than 10 s. Results for different extractants and various aqueous phase compositions will be presented and discussed

Nuclear track microfilters: gas separation ability and β-radiation stability

Nuclear track microfilters were produced by irradiating the polyimide foil UPILEX with highly energetic heavy ions and subsequent etching with sodium hypochlorite solution. Pore diameters and shape were investigated by scanning electron microscopy and a replica technique where the pores were electrochemically filled with metal. The results show that it is possible to form straight cylindrical pores with diameters in the range of 100 nm. The flow rate of air through the microfilters was determined. It turned out to be a linear function of the pore diameter at this pore size. With increasing pressure, the flow rate increases. At a certain level, the increase becomes non-linear, almost exponential. It can be assumed that this is due to stress-induced deformation of the polymer with an increase in the pore diameter. With the model system carbon monoxide and carbon dioxide the microfilters were tested for their ability for gas separation. Gas chromatographic measurements show that carbon monoxide penetrates faster through the microfilter, rendering gas separation possible. Possible applications of such microfilters for separating gases include radiation environment such as fusion reactors. For testing the β-radiation stability, the microfilters were stored in tritium gas. The microfilters appeared to be radiation resistant. After the storage time, no changes in the microfilter properties were found

Regulation of IgE production and airway reactivity by CD4(-)CD8(-) regulatory T cells

Pathogenesis and treatment of chronic pulmonary disease