Reaction of Selenium with Bromine in the Presence of Methyltriphenylphosphonium Bromide: Syntheses and Crystal Structures of [PMePh3]2[Se2Br6] and [PMePh3]2[SeBr6(SeBr2)2]

The brown crystals of [PMePh₃]₂[Se₂Br₆] ( 1 ) and red crystals of [PMePh₃]₂[SeBr₆(SeBr₂)₂] ( 2 ) were obtained when selenium and bromine reacted in the solution of acetonitrile in the presence of methyltriphenylphosphonium bromide. The crystal structures of 1 and 2 has been determined by the X‐ray methods and refined to R = 0.0373 for 2397 reflections and 0.0397 for 3417 reflections, respectively. The salt 1 crystallizes in the monoclinic space group P2₁/n with the cell dimensions a = 13.202(5) Å, b = 11.954(4) Å, c = 13.418(6) Å, β = 93.08(4)° (193(2)). The crystals of 2 are triclinic, space group with the cell dimensions a = 10.266(3) Å, b = 11.311(3) Å, c = 11.619(2) Å, α = 108.87(2)°, β = 105.72(2)°, γ = 99.40(2)° (193(2) K). In the solid state structure of 1 the dinuclear hexabromo‐diselenate(II) anion is centrosymmetric and consists of two distorted almost square planar SeBr₄ units sharing a common edge through two μ‐bridging Br atoms. The terminal Se^II–Br bonds are 2.3984(11) and 2.4273(11) Å, whereas the bridging μBr–Se^II bonds are 2.7817(11) and 2.9081(12) Å. In the solid state the trinuclear [SeBr₆(SeBr₂)₂]^2? anion of 2 is centrosymmetric too and contains a nearly regular [SeBr₆] octahedron where the four equatorial bromo ligands each have developed bonds to the Se^II atoms of the SeBr₂ molecules. The contacts between the bridging bromo and the Se^II atoms of the SeBr₂ molecules are 3.0603(15) and 3.1043(12) Å, and can be interpreted as bonds of the donor‐acceptor type with the bridging bromo ligands as donors and the SeBr₂ molecules as acceptors. The Se^IV–Br distances are in the range 2.5570(9)–2.5773(11) Å and the Se^II–Br bond lengths in coordinated SeBr₂ molecules – 2.3411(12) and 2.3421(10) Å.     

Time-dependent density-functional theory in the projector augmented-wave method

We present the implementation of the time-dependent density-functional theory both in linear-response and in time-propagation formalisms using the projector augmented-wave method in real-space grids. The two technically very different methods are compared in the linear-response regime where we found perfect agreement in the calculated photoabsorption spectra. We discuss the strengths and weaknesses of the two methods as well as their convergence properties. We demonstrate different applications of the methods by calculating excitation energies and excited state Born-Oppenheimer potential surfaces for a set of atoms and molecules with the linear-response method and by calculating nonlinear emission spectra using the time-propagation method.     

Lorentz violation from the Higgs portal

We study bounds and signatures of models where the Higgs doublet has an inhomogeneous mass or vacuum expectation value, being coupled to a hidden sector that breaks Lorentz invariance. This physics is best described by a low-energy effective Lagrangian in which the Higgs speed-of-light is smaller than c; such effect is naturally small because it is suppressed by four powers of the inhomogeneity scale. The Lorentz violation in the Higgs sector is communicated at tree level to fermions (via Yukawa interactions) and to massive gauge bosons, although the most important effect comes from one-loop diagrams for photons and from two-loop diagrams for fermions. We calculate these effects by deriving the renormalization-group equations for the speed-of-light of the Standard Model particles. An interesting feature is that the strong coupling dynamically makes the speed-of-light equal for all colored particles.     

Coordination of pyridinethiols in gold(I) complexes

High-yield synthesis of gold(I) thionato complexes, bis(pyridine-2-thionato)gold(I) chloride (1) and bis(pyridine-4-thionato)gold(I) chloride (2), are described. According to their solid-state structures, a linear coordination of Au(I), equiplanar coordination of the ligands and two weak gamma-agostic interactions are found in both of these complexes despite of different relative positions of N and S atoms in the pyridinethionato ligands. Density functional theory calculations on 1 and 2 reproduce the observed X-ray structures. Even though the C-H...Au interactions of Au(I) and two pyridine moieties (2.83 and 2.88 A in 1 and 2.86 A in 2) are relatively weak, according to calculations they seem to provide further stabilization for the coordination and orientation of the ligands. In 1 the shortest Au...Au distances of 3.50 A indicate that aurophilic interactions, even though weak, are present in the solid state, whereas in 2 these interactions are absent.     

Effects of fibre-surface morphology on the mechanical properties of Porifera-inspired rubber-matrix composites

In this paper, mineralised organic fibre morphologies, inspired by the structures of Porifera (sponges) are correlated to the mechanical performance of fibre reinforced rubbers. The mineralised structures are rich in calcium carbonate and silica. These compounds nucleate and precipitate on the fibre surfaces yielding different morphologies as a function of mineral ion concentrations. Smaller mineralised precipitates manifestly improve the mechanical performance of composites while thicker precipitates enveloping the fibres give rise to inferior properties. Mechanisms and evidenced reasoning for these differences are reported herein.     

A PCA study to determine how features in meteorite reflectance spectra vary with the samples’ physical properties

Meteorites have advanced our knowledge of processes in the Solar System with the application of high precision instruments here on Earth. The study of asteroids, the source of most meteorites, has in turn given us knowledge regarding the large scale evolution of the Solar System. Using the complementary information that asteroids and meteorites give us the story of our cosmic backyard can be more easily read. One efficient way to link meteorites to asteroids is by matching their respective reflectance spectra. There have been few convincing matches because of observational and scale differences as well as an incomplete knowledge of the light scattering physics involved. To better interpret the reflectance data we need to know the dependencies of the reflectance on physical properties and develop techniques for better comparisons of data sets. For these purposes we utilise our own measurements of 26 different meteorites together with spectra available on the NASA PDS.We find that normalisation of reflectance at a wavelength between 1.1 and 1.3 μm gives the closest match of spectra from meteorites common to both data sets. The depth of the spectra bands deepens by similar amounts for different types of surface texture alterations i.e. rock to sawn surface, rock to polished surface and rock to powdered surface. Principal Component Analysis (PCA) is able to easily place carbonaceous chondrites, ordinary chondrites and achondrites into distinct groups using their reflectance spectra. We track the variation of spectral features in principal component space by using a set of meteorite spectra synthesised from mineral and elemental spectra. A spectral agent that reduces the reflectance at all wavelengths is required, in addition to olivine, pyroxene and carbon, to generate a set of synthesised spectra to match the distribution of measured spectra, in principal component space.     

Neutrino masses in supersymmetry: R-parity and leptogenesis

In the supersymmetric standard model of particle interactions, R-parity nonconservation is often invoked to obtain nonzero neutrino masses. We point out here that such interactions of the supersymmetric particles would erase any pre-existing lepton or baryon asymmetry of the universe before the electroweak phase transition through the B+L violating sphaleron processes. We also point out that all models of radiative generation of neutrino masses suffer from the same problem. We then show how neutrino masses may be obtained in supersymmetry (assuming R-parity conservation) together with successful leptogenesis and predict the possible existence of new observable particles.     

Giant optical activity in quasi-two-dimensional planar nanostructures

We examine the spectral dependence in the visible frequency range of the polarization rotation of two-dimensional gratings consisting of chiral gold nanostructures with subwavelength features. The gratings, which do not diffract, are shown to exhibit giant specific rotation (approximately 10(4) degrees/mm) of polarization in direct transmission at normal incidence. The rotation is the same for light incident on the front and back sides of the sample. Such reciprocity indicates three dimensionality of the structure arising from the asymmetry of light-plasmon coupling at the air-metal and substrate-metal interfaces. The structures thus enable polarization control with quasi-two-dimensional planar objects. However, in contradiction with recently suggested interpretation of experiments on larger scale but otherwise similar structures, the observed polarization phenomena violate neither reciprocity nor time-reversal symmetry.     

A problem on heat conduction in an insulated wire solved by numerical inverse Laplace transform

A problem of transient heat conduction in an insulated wire is solved by use of Laplace transform and numerical inversion. The problem is solved for the radiation boundary condition and also for the boundary condition of no heat flux through the outer surface of the insulation. The results are presented both numerically with four significant figures and graphically. Asymptotic expansions are derived for small and large values of the time variable. The numerical inversion of the Laplace transform is checked by comparison with the asymptotic expansions and with the numerical results obtained by a numerical inversion formula utilizing one more abscissa than the previous one.