Ground-state electric quadrupole moment of 31Al

Ground-state electric quadrupole moment of 31Al (I =5/2+, T_1/2 = 644(25) ms) has been measured by means of the beta-NMR spectroscopy using a spin-polarized 31Al beam produced in the projectile fragmentation reaction. The obtained Q moment, |Q_exp(31Al)| = 112(32)emb, are in agreement with conventional shell model calculations within the sd valence space. Previous result on the magnetic moment also supports the validity of the sd model in this isotope, and thus it is concluded that 31Al is located outside of the island of inversion.Comment: 5 page

Tipping the balance: theoretical interrogation of divergent extended heterolytic fragmentations.

Herein we interrogate a type of heterolytic fragmentation reaction called a 'divergent fragmentation' using density functional theory (DFT), natural bond orbital (NBO) analysis, ab initio molecular dynamics (AIMD), and external electric field (EEF) calculations. We demonstrate that substituents, electrostatic environment and non-statistical dynamic effects all influence product selectivity in reactions that involve divergent fragmentation pathways. Direct dynamics simulations reveal an unexpected post-transition state bifurcation (PTSB), and EEF calculations suggest that some transition states for divergent pathways can, in principle, be selectively stabilized if an electric field of the correct magnitude is oriented appropriately

Synthetic Studies toward Biologically Active Quinones and Alkaloids

Part 1 describes the synthesis and biological evaluation of small-molecule phosphatase inhibitors. The targets for the synthesized compounds are mainly Cdc25 phosphatases, which play a key role in regulating cell cycle and are often over-expressed in cancers. Highlights of the synthesis are the amide bond formation, the synthesis of secondary amines via o-Ns chemistry, the ring opening of the lactam by the amine, the preparation of various (iso)quinolinediones and the substitution reactions of (iso)quinolinediones with amines and thiols. The synthesis and reaction of isoquinonlinediones are particularly highlighted in the total synthesis of caulibugulones A-E. Biological assays established the (iso)quinolinediones as new phosphatase inhibitors with considerable selectivity against the Cdc25 family of DSPases.Part 2 describes the synthetic studies toward the total synthesis of parvistemonine, which represents one of the most challenging synthetic targets among Stemona alkaloids. The studies are mainly focused on the development of a fragmentation strategy aimed at the total synthesis of parvistemonine. Highlights of these studies are the synthesis of vinyl azides, the fragmentation reaction of tertiary alcohols and the use of the trimethylsilyl-methylene group as a directing group in the fragmentation reaction. These studies demonstrate a novel vinylogous azido alcohol fragmentation reaction in simple model systems and a regioselective fragmentation reaction of hydroxy indolines

Shape and structure of N=Z 64Ge; Electromagnetic transition rates from the application of the Recoil Distance Method to knock-out reaction

Transition rate measurements are reported for the first and the second 2+ states in N=Z 64Ge. The experimental results are in excellent agreement with large-scale Shell Model calculations applying the recently developed GXPF1A interactions. Theoretical analysis suggests that 64Ge is a collective gamma-soft anharmonic vibrator. The measurement was done using the Recoil Distance Method (RDM) and a unique combination of state-of-the-art instruments at the National Superconducting Cyclotron Laboratory (NSCL). States of interest were populated via an intermediate-energy single-neutron knock-out reaction. RDM studies of knock-out and fragmentation reaction products hold the promise of reaching far from stability and providing lifetime information for excited states in a wide range of nuclei

Exploiting neutron-rich radioactive ion beams to constrain the symmetry energy

The Modular Neutron Array (MoNA) and 4 Tm Sweeper magnet were used to measure the free neutrons and heavy charged particles from the radioactive ion beam induced 32Mg + 9Be reaction. The fragmentation reaction was simulated with the Constrained Molecular Dynamics model(CoMD), which demonstrated that the of the heavy fragments and free neutron multiplicities were observables sensitive to the density dependence of the symmetry energy at sub-saturation densities. Through comparison of these simulations with the experimental data constraints on the density dependence of the symmetry energy were extracted. The advantage of radioactive ion beams as a probe of the symmetry energy is demonstrated through examination of CoMD calculations for stable and radioactive beam induced reactions

Magnetic Moment of the Fragmentation Aligned 61Fe(9/2)+ Isomer

We report on the g factor measurement of the isomer in $^{61}Fe$ ($E^{*}=861 keV$). The isomer was produced and spin-aligned via a projectile-fragmentation reaction at intermediate energy, the Time Dependent Perturbed Angular Distribution (TDPAD) method being used for the measurement of the g factor. For the first time, due to significant improvements of the experimental technique, an appreciable residual alignment of the isomer has been observed, allowing a precise determination of its g factor: $g=-0.229(2)$. Comparison of the experimental g factor with shell-model and mean field calculations confirms the $9/2^+$ spin and parity assignments and suggests the onset of deformation due to the intrusion of Nilsson orbitals emerging from the $\nu g_{9/2}$.Comment: 4 figures. Submitted to Phys. Rev. Let

Computational Study of the Photochemical Fragmentation of Hydantoin

The mechanism of the photochemical fragmentation reaction is investigated theoretically using the model system, hydantoin, using the CAS(22,16)/6-31G(d) and MP2-CAS-(22,16)/6-311G(d)//CAS(22,16)/6-31G(d) methods. The model investigation demonstrates that the preferred reaction route for the photofragmentation reaction is as follows: hydantoin → Franck-Condon region → conical intersection → fragment photoproducts (i.e., CO, isocyanic acid, and methylenimine). The theoretical finding additionally suggests that no organic radicals exist during the fragmentation reaction. Moreover, due to the high activation energy, the theoretical evidences suggest that it would be difficult to yield the three fragments under the thermal reaction. All the above theoretical observations are consistent with the available experimental results