Study of Quasielastic Barrier Distributions as a Step towards the Synthesis of Superheavy Elements with Hot Fusion Reactions

The excitation functions for quasielastic scattering of Ne22+Cm248, Mg26+Cm248, and Ca48+U238 are measured using a gas-filled recoil ion separator. The quasielastic barrier distributions are extracted for these systems and are compared with coupled-channel calculations. The results indicate that the barrier distribution is affected dominantly by deformation of the actinide target nuclei, but also by vibrational or rotational excitations of the projectile nuclei, as well as neutron transfer processes before capture. From a comparison between the experimental barrier distributions and the evaporation residue cross sections for Sg (Z=106), Hs (108), Cn (112), and Lv (116), it is suggested that the hot fusion reactions take advantage of a compact collision, where the projectile approaches along the short axis of a prolately deformed nucleus. A new method is proposed to estimate the optimum incident energy to synthesize unknown superheavy nuclei using the barrier distribution.This research was partially supported by a Grantin-Aid for Specially Promoted Research, 19002005, from the Ministry of Education, Culture, Sports, Science and Technology of Japan, and by the U.S. DOE Office of Nuclear Physics. T. T. thanks the RIKEN Junior Research Associate Program

Chirality and Polarity in the f-Block Borates M4_{4} [B16_{16} O 26_{26} (OH) 4_{4} (H 2_{2} O) 3_{3} Cl 4_{4} ] (M=Sm, Eu, Gd, Pu, Am, Cm, and Cf)

The reactions of trivalent lanthanides and actinides with molten boric acid in high chloride concentrations result in the formation of M4[B16O26(OH)4(H2O)3Cl4] (M=Sm, Eu, Gd, Pu, Am, Cm, Cf). This cubic structure type is remarkably complex and displays both chirality and polarity. The polymeric borate network forms helical features that are linked via two different types of nine-coordinate f-element environments. The f–f transitions are unusually intense and result in dark coloration of these compounds with actinides

Emergence of californium as the second transitional element in the actinide series

vi+126hlm;14x21c

Electronic Structure and Properties of Berkelium Iodates

The reaction of ²⁴⁹Bk­(OH)₄ with iodate under hydrothermal conditions results in the formation of Bk­(IO₃)₃ as the major product with trace amounts of Bk­(IO₃)₄ also crystallizing from the reaction mixture. The structure of Bk­(IO₃)₃ consists of nine-coordinate Bk^III cations that are bridged by iodate anions to yield layers that are isomorphous with those found for Am^III, Cf^III, and with lanthanides that possess similar ionic radii. Bk­(IO₃)₄ was expected to adopt the same structure as M­(IO₃)₄ (M = Ce, Np, Pu), but instead parallels the structural chemistry of the smaller Zr^IV cation. Bk^III–O and Bk^IV–O bond lengths are shorter than anticipated and provide further support for a postcurium break in the actinide series. Photoluminescence and absorption spectra collected from single crystals of Bk­(IO₃)₄ show evidence for doping with Bk^III in these crystals. In addition to luminescence from Bk^III in the Bk­(IO₃)₄ crystals, a broad-band absorption feature is initially present that is similar to features observed in systems with intervalence charge transfer. However, the high-specific activity of ²⁴⁹Bk (<i>t</i>_1/2 = 320 d) causes oxidation of Bk^III and only Bk^IV is present after a few days with concomitant loss of both the Bk^III luminescence and the broadband feature. The electronic structure of Bk­(IO₃)₃ and Bk­(IO₃)₄ were examined using a range of computational methods that include density functional theory both on clusters and on periodic structures, relativistic <i>ab initio</i> wave function calculations that incorporate spin–orbit coupling (CASSCF), and by a full-model Hamiltonian with spin–orbit coupling and Slater–Condon parameters (CONDON). Some of these methods provide evidence for an asymmetric ground state present in Bk^IV that does not strictly adhere to Russel–Saunders coupling and Hund’s Rule even though it possesses a half-filled 5<i>f</i> ⁷ shell. Multiple factors contribute to the asymmetry that include 5<i>f</i> electrons being present in microstates that are not solely spin up, spin–orbit coupling induced mixing of low-lying excited states with the ground state, and covalency in the Bk^IV–O bonds that distributes the 5<i>f</i> electrons onto the ligands. These factors are absent or diminished in other <i>f</i>⁷ ions such as Gd^III or Cm^III

Unusual structure, bonding and properties in a californium borate

The participation of the valence orbitals of actinides in bonding has been debated for decades. Recent experimental and computational investigations demonstrated the involvement of 6p, 6d and/or 5f orbitals in bonding. However, structural and spectroscopic data, as well as theory, indicate a decrease in covalency across the actinide series, and the evidence points to highly ionic, lanthanide-like bonding for late actinides. Here we show that chemical differentiation between californium and lanthanides can be achieved by using ligands that are both highly polarizable and substantially rearrange on complexation. A ligand that suits both of these desired properties is polyborate. We demonstrate that the 5f, 6d and 7p orbitals are all involved in bonding in a Cf(III) borate, and that large crystal-field effects are present. Synthetic, structural and spectroscopic data are complemented by quantum mechanical calculations to support these observations