Exotic nuclei produced by heavy-ions induced fission

About thirty nuclei in theA≈100 mass region have been produced as fission fragments following the fusion-evaporation reactions^28,30Si+¹⁷⁶Yb at 145 MeV bombarding energy. These nuclei have been individually identified from their γ-ray cascades detected with the Eurogam2 array. The level schemes of several stable or neutron-rich nuclei have been extended to higher spins. From cross coincidences between transitions in complementary fragments, γ-rays de-exciting high-spin states of new isotopes can be identified and some aspects of the fission mechanism can be analyzed.     

Microwave Plasmas at Atmospheric Pressure

Microwave plasmas at atmospheric pressure are used for surface treatments like for example cleaning, sterilization or decontamination purposes, for a pre‐treatment to increase the adhesion of lacquer, paint, or glue, and for the deposition of different kind of layers and coatings. Micro plasma jets can also be applied for biomedical applications and for treatment of small and complex geometries like for example the inside of capillaries. Larger plasma torches which exhibit higher gas temperatures can also be used for chemical syntheses like waste gas decomposition, methane pyrolysis, or carbon dioxide dissociation and for plasma spraying purposes. In the present publication an overview on the development and the investigation of the operating principle of two atmospheric pressure microwave plasma torches at frequencies of 2.45 GHz and 915 MHz will be presented. The plasma sources are based on a cylindrical resonator combined with coaxial structures. To explain how these plasma sources work, simulations of the electric field distribution will be discussed. Furthermore, some physical characteristics of an air and an Ar/H2 atmospheric plasma like gas temperatures, excitation temperatures and densities as well as the heating of the plasma by the microwave will be investigated. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Numerical simulation and laser-based imaging of mixture formation, ignition, and soot formation in a diesel spray

Laser-based imaging of fuel vapor distribution, ignition, and soot formation in diesel sprays was carried out in a high-pressure, high-temperature spray chamber under conditions that correspond to temperature and pressure in a diesel engine. Rayleigh scattering and laser-induced incandescence are used to image fuel density and soot volume fraction. The experimental results provide data for comparison with numerical simulations. An interactive cross-sectionally averaged spray model based on Eulerian transport equations was used for the simulation of the spray, and the turbulence-chemistry interaction was modeled with the representative interactive flamelet (RIF) concept. The flamelet calculation is coupled to the Kiva3V computational fluid dynamics (CFD) code using the scalar dissipation rate and pressure as an input to the RIF-code. The flamelet code computes the instationary flamelet profiles for every time step. These profiles were integrated over mixture fraction space using a prescribed β-PDF to obtain mean values, which are passed back to the CFD-code. Thereby, the temperature and the relevant species in each CFD-cell were obtained. The fuel distribution, the average ignition delay as well as the location of ignition are well predicted by the simulation. Furthermore, simulations show that the experimentally observed injection-to-injection variations in ignition delay are due to temperature inhomogeneities. Experimental and simulated spatial soot and fuel vapor density distributions are compared during and after second stage ignition.     

The optimal shape of a pipe

In shape optimization, recently the question arose, whether or not the cylindrical pipe has the optimal shape for the transport of an incompressible fluid. In this short note, a proof will be presented that a cylindrical pipe with Poiseuille’s flow inside indeed is optimal for the transportation of an incompressible fluid under the criterion “energy dissipated by the fluid.” The proof reduces the problem to the minimization of a two-dimensional Dirichlet’s integral. This simpler problem can be solved with a symmetrization argument.     

Thermal decomposition of trimethylgallium Ga(CH3)3: a shock-tube study and first-principles calculations

The thermal decomposition of Ga(CH3)3 has been studied both experimentally in shock-heated gases and theoretically within an ab-initio framework. Experiments for pressures ranging from 0.3 to 4 bar were performed in a shock tube equipped with atomic resonance absorption spectroscopy (ARAS) for Ga atoms at 403.3 nm. Time-resolved measurements of Ga atom concentrations were conducted behind incident waves as well as behind reflected shock waves at temperatures between 1210 and 1630 K. The temporal variation in Ga-atom concentration was described by a reaction mechanism involving the successive abstraction of methyl radicals from Ga(CH3)3 (R1), Ga(CH3)2 (R2), and GaCH3 (R3), respectively, where the last reaction is the rate-limiting step leading to Ga-atom formation. The rate constant of this reaction (R3) was deduced from a simulation of the measured Ga-atom concentration profiles using thermochemical data from ab-initio calculations for the reactions R1 and R2 as input. The Rice-Ramsperger-Kassel-Marcus (RRKM) method including variational transition state theory was applied for reaction R3 assuming a loose transition state. Structural parameters and vibrational frequencies of the reactant and transition state required for the RRKM calculations were obtained from first-principles simulations. The energy barrier E3(0) of reaction R3, which is the most sensitive parameter in the calculation, was adjusted until the RRKM rate constant matched the experimental one and was found to be E(0) = 288 kJ/mol. This value is in a good agreement with the corresponding ab-initio value of 266 kJ/mol. The rate constant of reaction R3 was found to be k 3/(cm(3) mol(-1)s(-1)) = 2.34 x 10(11) exp[-23330(K/ T)].     

Synthesis and Structure of Monomeric,Trimeric, and Mixed Phenylcyanamides

In a new synthetic approach phenylcyanamide (Hpca) was synthesized by methylation of phenylthiourea followed by a basic work‐up. All products along the synthetic route have been fully characterized by means of NMR, IR, and X‐ray studies. The first structural report of neutral mixed crystals of phenylcyanamide containing monomeric and trimeric Hpca is presented. Examination of these intriguing mixed crystals revealed the formation of distinct layers of monomeric and trimeric Hpca. These layers are interconnected by weak hydrogen bonds. The trimer represents triphenylisomelamine, which readily isomerizes to the triphenylmelamine in the melt, in accord with computations at the B3LYP level, indicating an exothermic process (ΔH=?49.4 kcal mol^?1). Pure trimeric Hpca (triphenylisomelamine) was obtained either by recrystallization of the mixed crystals from boiling water or by trimerization of monomeric Hpca in isopropanol for 12 h under reflux conditions. For comparison tritylcyanamide (Htca) and potassium phenylcyanamide as an [18]crown‐6 complex [K([18]crown‐6)pca] have been synthesized, and the solid‐state structures were determined using X‐ray diffraction techniques. The thermal behavior was studied by thermo‐analytical experiments. In agreement with the experimental results, computations predict an exothermic cyclotrimerization process for Hpca (ΔH=?41.3 kcal mol^?1).     

Ultrafast ring-closure reaction of photochromic indolylfulgimides studied with UV-pump-IR-probe spectroscopy

The ring-opening and ring-closure reactions of a photochromic indolylfulgimide are investigated with femtosecond vibrational spectroscopy. Spectral signatures due to excited-state decay and vibrational cooling are seen in the mid-IR region. For the ring-opening reaction triggered with visible pulses, a lifetime of the excited electronic state of 4 ps was obtained in polar solution. In a nonpolar solvent, this time constant is reduced to 2 ps. The ring-closure reaction induced with UV pulses displays an excited-state lifetime and thus a building of the photoproduct of roughly 0.5 ps. For all processes, the subsequent cooling occurs on a 15-ps time scale lasting up to approximately 50 ps. The time-resolved IR measurements do not support the existence of any long-living intermediate states.     

Synthesis of mesoporous silicas in alkaline and acidic media using the systems cetyltrimethylammonium tosylate (CTAT)-Pluronic F127 triblock copolymer and CTAT-Pluronic F68 triblock copolymer as templates

Mesoporous silica materials were synthesized in alkaline and acidic media, using cetyltrimethylammonium tosylate (CTAT), Pluronic triblock copolymers F127 and F68, and mixtures of CTAT with each copolymer in order to investigate the effects of pH, surfactant concentration, and CTAT/triblock copolymer molar ratios on the morphology and texture of the synthesized materials. The results show that the kind of mesoporous materials and their pore size can be tuned by changing not only the pH but also the proportion of components and the nature of the copolymer. In alkaline synthesis, microscopic bicontinuous materials are obtained, which are composed by nanoscopic plate-like particles having slit-shaped pores. In acidic synthesis, on the contrary, monolithic silicas are obtained. These materials are also composed by nanoscopic plate-like particles having slit-shaped pores, although in some cases, the microscopic structures are formed by fused spherical particles. The inclusion of the triblock copolymer in the template composition causes a transformation from a bimodal to a monomodal pore size distribution, leading to small and nearly round pores which are probably formed by copolymer or copolymer-CTAT mixed micelles. The differences between the systems synthesized by CTAT-Pluronic F127 and CTAT-Pluronic F68 are explained on the basis of the different interactions between each copolymer and CTAT.     

Odd-even effects in charge transport across self-assembled monolayers

This paper compares charge transport across self-assembled monolayers (SAMs) of n-alkanethiols containing odd and even numbers of methylenes. Ultraflat template-stripped silver (Ag(TS)) surfaces support the SAMs, while top electrodes of eutectic gallium-indium (EGaIn) contact the SAMs to form metal/SAM//oxide/EGaIn junctions. The EGaIn spontaneously reacts with ambient oxygen to form a thin (～1 nm) oxide layer. This oxide layer enables EGaIn to maintain a stable, conical shape (convenient for forming microcontacts to SAMs) while retaining the ability to deform and flow upon contacting a hard surface. Conical electrodes of EGaIn conform (at least partially) to SAMs and generate high yields of working junctions. Ga(2)O(3)/EGaIn top electrodes enable the collection of statistically significant numbers of data in convenient periods of time. The observed difference in charge transport between n-alkanethiols with odd and even numbers of methylenes--the "odd-even effect"--is statistically discernible using these junctions and demonstrates that this technique is sensitive to small differences in the structure and properties of the SAM. Alkanethiols with an even number of methylenes exhibit the expected exponential decrease in current density, J, with increasing chain length, as do alkanethiols with an odd number of methylenes. This trend disappears, however, when the two data sets are analyzed together: alkanethiols with an even number of methylenes typically show higher J than homologous alkanethiols with an odd number of methylenes. The precision of the present measurements and the statistical power of the present analysis are only sufficient to identify, with statistical confidence, the difference between an odd and even number of methylenes with respect to J, but not with respect to the tunneling decay constant, β, or the pre-exponential factor, J(0). This paper includes a discussion of the possible origins of the odd-even effect but does not endorse a single explanation.