Anionic polymerization of butadiene: A MNDO study of the potential energy surface of the propagation reaction in polar and non-polar media

The anionic polymerization of butadiene, to both the 1,2- and 1,4-addition products, is an important industrial process. It is known that the reaction can be steered to either the 1,2- or 1,4-product by the addition, or absence, of a complexing solvent such as ether. The goals of the current study were to map the MNDO Potential Energy Surfaces (PES) of the propagation reactions both in the presence and absence of dimethyl ether to gain insight into the factors influencing the reaction's selectivity. Single point ab initio calculations at the DZP level were run on all reactants, products and transition states as a cross check on the MNDO results.     

Homometric polytypes

A new theorem on homometric polytypes is presented. Examples of homometric close-packed structures and MX₂-polytypes are given. The method derived may be used to construct homometric n-tuplets by means of decomposition procedures.     

The Duotron,Can It Solve the Solar Neutrino Problem?

At a summary of the four present measurements for the solar neutrino problem one receives for the quotient of the number of the really observed events and the theoretically by the standard solar model exspected value the result This says that in the mean only 33.25% with a possible mistake of 19.25% of the exspected solar neutrinos have been observed. If one goes out from the assumption, that the attempts hitherto proposed for the solution of the problem on the solar neutrino deficits as to be regarded as very unsatisfactory on the one side, while on the other the neutrinos of the β-decay may not exist at all, this looks very troublesome. But there is another possibility of a new interpretation. One has to consider, that in connection with each theoretically until now assumed neutrino of β-decay at the solar p-p- and all joined following fusion -processes precisely one positron will be produced. Exactly this particle will with the probability 1/2 in a triplett state of fixing with an electron of the solar centre plasma at a binding energy of −2029.7 eV create an electric-neutral duotron. This particle assumes fully, inclusive the very welcome factor 1/2, the rǒle of the theoretically dispensable neutrino. This can be regarded as the solution of the solar neutrino-problem.     

Evolution and Trade-Off Dynamics of Functional Load

Functional load (FL) quantifies the contributions by phonological contrasts to distinctions made across the lexicon. Previous research has linked particularly low values of FL to sound change. Here, we broaden the scope of enquiry into FL to its evolution at higher values also. We apply phylogenetic methods to examine the diachronic evolution of FL across 90 languages of the Pama–Nyungan (PN) family of Australia. We find a high degree of phylogenetic signal in FL, indicating that FL values covary closely with genealogical structure across the family. Though phylogenetic signals have been reported for phonological structures, such as phonotactics, their detection in measures of phonological function is novel. We also find a significant, negative correlation between the FL of vowel length and of the following consonant—that is, a time-depth historical trade-off dynamic, which we relate to known allophony in modern PN languages and compensatory sound changes in their past. The findings reveal a historical dynamic, similar to transphonologization, which we characterize as a flow of contrastiveness between subsystems of the phonology. Recurring across a language family that spans a whole continent and many millennia of time depth, our findings provide one of the most compelling examples yet of Sapir’s ‘drift’ hypothesis of non-accidental parallel development in historically related languages.     

Combined use of small-angle neutron scattering and atom probe tomography for the analysis of precipitates in a Fe-15 m% Co-25 m% Mo alloy

Atom probe tomography (APT) measurements were conducted to analyze nm-sized precipitates in a Fe-25 m% Co-15 m% Mo model alloy. Calculation of isoconcentration surfaces and application of cluster-search algorithms yielded the chemical compositions of matrix and precipitates. Small-angle neutron scattering (SANS) was performed in order to calculate the ratio of magnetic to nuclear scattering. This so-called A-ratio was compared with values calculated from the chemical information derived from the atom probe data. For this, the magnetism of the precipitates has to be taken into account. Ab-initio studies have been carried out to determine the magnetic moment of the precipitate phase. The results show that the extremely fine precipitates are ferromagnetic and exhibit near-equilibrium composition. In the very early stage of decomposition, however, the composition is different from near-equilibrium. The influences of the magnetism of the precipitates as well as of artifacts from atom probe measurements on the obtained results are discussed.     

Mechanical Behavior of Polymer Gels for RDCs and RCSAs Collection: NMR Imaging Study of Buckling Phenomena

Anisotropic NMR parameters, such as residual dipolar couplings (RDCs), residual chemical shift anisotropies (RCSAs) and residual quadrupolar couplings (RQCs or Δν_Q), appear in solution‐state NMR when the molecules under study are subjected to a degree of order. The tunable alignment by reversible compression/relaxation of gels (PMMA and p‐HEMA) is an easy, user‐friendly, and very affordable method to measure them. When using this method, a fraction of isotropic NMR signals is observed in the NMR spectra, even at a maximum degree of compression. To explain the origin of these isotropic signals we decided to investigate their physical location inside the NMR tube using deuterium 1D imaging and MRI micro‐imaging experiments. It was observed that after a certain degree of compression the gels start to buckle and they generate pockets of isotropic solvent, which are never eliminated. The amount of buckling depends on the amount of cross‐linker and the length of the gel.     

Helfrich repulsion and dynamical phase separation of multicomponent lipid bilayers

Thermal fluctuations of surfactant bilayers in an aqueous solution produce an effective, long-range repulsion that can lead to a continuous unbinding transition. We report on an optical interferometry study of the thermal fluctuations of multicomponent bilayers close to the unbinding transition. We find that, in contrast to the case of single-component bilayers, the thermal fluctuation spectrum of multicomponent bilayers does not agree with a continuous unbinding transition but instead indicates the proximity of an unbinding tricritical point.     

Two-component Bose-Einstein condensates with a large number of vortices

We consider the condensate wave function of a rapidly rotating two-component Bose gas with an equal number of particles in each component. If the interactions between like and unlike species are very similar (as occurs for two hyperfine states of (87)Rb or (23)Na) we find that the two components contain identical rectangular vortex lattices, where the unit cell has an aspect ratio of sqrt[3], and one lattice is displaced to the center of the unit cell of the other. Our results are based on an exact evaluation of the vortex lattice energy in the large angular momentum (or quantum Hall) regime.     

Quantum-limited noise performance of a mode-locked laser diode

Low-noise operation of a 9-GHz hybridly mode-locked laser diode is demonstrated. The integrated timing jitter was 47 fs (10 Hz to 10 MHz) and 86 fs (10 Hz to 4.5 GHz), with a pulse width of 6.7 ps. The noise performance as a function of filter bandwidth and oscillator noise is also addressed.     

Self-stabilized passive, harmonically mode-locked stretched-pulse erbium fiber ring laser

We have studied a passive, harmonically mode-locked stretched-pulse erbium fiber ring laser with net positive dispersion that is self-stabilized by gain depletion and electrostriction. Periodic pulses with supermode suppression of >75 dB and picosecond jitter are achieved. The pulses are compressible to 125 fs by external chirp compensation. The repetition rate is 220 MHz, and the average power is as high as 80 mW.