Influence of solvent and weak C-H...O contacts in the self-assembled [Pt2M4{CC(3-OMe)C6H4}8] (M = Cu, Ag) clusters and their role in the luminescence behavior

New alkynyl complexes [Pt2M4{CC(3-OMe)C6H4}8] (M = Ag 1, Cu 2) have been synthesized and their structures and properties compared to those of related [Pt2M4(CCPh)8] compounds. For the Pt-Ag derivatives, the X-ray structures of the discrete yellow solvate monomer, [Pt2Ag4{CC(3-OMe)C6H4}8].2THF ([1.2THF]), and the dark garnet unsolvated polymeric form, [Pt2Ag4{CC(3-OMe)C6H4}8](infinity) ([1](infinity)), are presented. The yellow form ([1.2THF]) exhibits a distorted octahedral geometry of the metal centers with the platinum atoms mutually trans and the four silver atoms in the equatorial plane. Pairs of Ag atoms are weakly bridged by THF molecules [mu-Ag2...O(THF)]. The garnet form ([1](infinity)) has an unprecedented infinite stacked chain of octahedral clusters linked by short Pt...Pt bonds (3.1458(8) A). In both forms, different types of weak C-H...O (OMe) hydrogen bonds are observed. For comparative purposes, we have also provided the crystal structures of the yellow monomer form, [Pt2Ag4-(CCPh)8].CHCl3, and the red dimer form, [Pt2Ag4(CCPh)8]2 (Pt-Pt 3.221(2) A). These clusters display intense photoluminescence in both solution and the solid state, at room temperature and 77 K. The emission observed for the yellow form [1.2THF] in the solid state is assigned to a 3MLM'CT [Pt(d)/pi(CCR) --> Pt(p(z))/Ag(sp)/pi(CCR)] state modified by Pt...Ag, Ag...Ag, and Ag...(THF) contacts. However, in the garnet form [1](infinity) and in 2, the emissions are related to the axial Pt-Pt bonds and are assigned as phosphorescence from a metal-metal-to-ligand charge-transfer (3MMLCT) excited state ([1](infinity)), or an admixture of a metal-metal (Pt-Pt) centered 3(dsigmap(z)sigma) and 3MMLCT excited state (2). For 1, a remarkable quenching and a shift to higher energies in the emission is observed on changing from CH2Cl2 to THF, and for both 1 and 2, the emission spectra at 77 K varies with the concentration, showing their tendency to stack even in glass.     

Noise reduction in ultrasonic NDT using undecimated wavelet transforms

Translation-invariant wavelet processing is applied to grain noise reduction in ultrasonic non-destructive testing of materials. In particular, the undecimated wavelet transform (UWT), which is essentially a discrete wavelet transform (DWT) that avoids decimation, is used. Two different UWT processors have been specifically developed for that purpose, based on two UWT implementation schemes: the "à trous" algorithm and the cycle-spinning scheme. The performance of these two UWT processors is compared with that of a classical DWT processor, by using synthetic grain noise registers and experimental pulse-echo NDT traces. The synthetic ultrasonic traces have been generated by an own-developed frequency-domain model that includes frequency dependence in both material attenuation and scattering. The experimental ultrasonic traces have been obtained by inspecting a piece of carbon-fiber reinforced plastic composite in which we have mechanized artificial flaws. Decomposition level-dependent thresholds, which are suitable for correlated noise, are specifically determined in all cases. Soft thresholding, Daubechies db6 mother wavelet and the three well-known threshold selection rules, Universal, Minimax and SURE, are applied to the different decomposition levels. The performance of the different de-noising procedures for single echo detection has been comparatively evaluated in terms of signal-to-noise ratio enhancement.     

Pulsed, high-power LED illumination for tomographic particle image velocimetry

This paper investigates the use of high-power light-emitting diode (LED) illumination for tomographic particle image velocimetry (PIV) as an alternative to traditional laser-based illumination. Modern solid-state LED devices can provide averaged radiant power in excess of 10 W and by operating the LED with short high current pulses theoretical pulse energies up to several tens of mJ can be achieved. In the present work, a custom-built drive circuit is used to drive a Luminus PT-120 high-power LED at pulsed currents of up to 150 A and 1 μs duration. Volumetric illumination is achieved by directly projecting the LED into the flow to produce a measurement volume of ≈3–4 times the size of the LED die. The feasibility of the volumetric LED illumination is assessed by performing tomographic PIV of homogenous, grid-generated turbulence. Two types of LEDs are investigated, and the results are compared with measurements of the same flow using pulsed Nd:YAG laser illumination and DNS data of homogeneous isotropic turbulence. The quality of the results is similar for both investigated LEDs with no significant difference between the LED and Nd:YAG illumination. Compared with the DNS, some differences are observed in the power spectra and the probability distributions of the fluctuating velocity and velocity gradients. These differences are attributed to the limited spatial resolution of the experiments and noise introduced during the tomographic reconstruction (i.e. ghost particles). The uncertainty in the velocity measurements associated with the LED illumination is estimated to approximately 0.2–0.3 pixel for both LEDs, which compares favourably with similar tomographic PIV measurements of turbulent flows. In conclusion, the proposed high-power, pulsed LED volume illumination provides accurate and reliable tomographic PIV measurements in water and presents a promising technique for flow diagnostics and velocimetry.     

Nonequatorial circular orbits of spinning particles in the Schwarzschild–de Sitter background

In this paper analytical solutions of the Mathisson–Papapetrou equations that describe nonequatorial circular orbits of a spinning particle in the Schwarzschild–de Sitter background are studied, and the role of the cosmological constant is emphasized. It is shown that generally speaking a highly relativistic velocity of the particle is a necessary condition of motion along this type of orbits, with an exception of orbits locating close to the position of the static equilibrium, where low velocities are possible as well. Depending on the correlation between the spin orientation of the particle and its orbital velocity some of the possible nonequatorial circular orbits exist due to the repulsive action on the particle caused by the spin–gravity coupling and the others are caused by the attractive action. Here values of the energy of the particle on the corresponding orbits are also analyzed.     

On binding energy of trions in bulk materials

We study the negatively $T^{?}$ and positively $T^{+}$ charged trions in bulk materials in the effective mass approximation within the framework of a potential model. The binding energies of trions in various semiconductors are calculated by employing Faddeev equation in configuration space. Results of calculations of the binding energies for $T^{?}$ are consistent with previous computational studies and are in reasonable agreement with experimental measurements, while the $T^{+}$ is unbound for all considered cases. The mechanism of formation of the binding energy of trions is analyzed by comparing contributions of a mass-polarization term related to kinetic energy operators and a term related to the Coulomb repulsion of identical particles.     

On transmittance and localization of the electromagnetic wave in two-dimensional graphene-based photonic crystals

Two-dimensional graphene-based photonic crystal (GPC) formed by a periodic array of the homogeneous dielectric cylinders etched in the alternating graphene and dielectric layers and its inverse counterpart are considered. The transmittance of the photonic crystal is obtained. The waveguide due to the localization of the electromagnetic wave on the lattice defect that breaks the translational symmetry of the GPC of two different topologies is studied. The different topologies of GPC are characterized by different photonic band structures with different widths of photonic band gaps (PBG) and provide different frequencies for the localized electromagnetic wave due to the defect. The frequencies of the localized mode for both type of the GPC, located inside the lowest PBG, are in the range of THz or tens of THz depending on the topology of the GPC. It is shown that the photonic band gap always can be tuned by changing the chemical potential of graphene to provide formation of the localized photonic mode due to the defect. The technological advantages of the GPC, as well as the opportunity to tune the PBG and the frequency of the localized electromagnetic wave in the terahertz region of spectrum for the GPC are discussed.     

Transmission of the spin-spin coupling constants through hydrogen bonds in ammonia clusters

Spin-spin coupling constants are reported using six ab initio and fifteen DFT methods for dimers and larger clusters of ammonia. An analysis of components (Fermi contact, spin dipole, paramagnetic spin-orbit, and diamagnetic spin-orbit) of more relevant coupling constants ¹J_NH′, ^1hJ_NH′ and ^2hJ_NN has been carried out. Fermi contact is the dominant term in the total value for all constants. For dimers, a relationship between the addition of direct and intermolecular coupling constants gives the direct constants of monomer. From the comparison of all ab initio and DFT methods for dimers, SOPPA(CCSD) and S55VWN5 methods are, respectively, more reliable taking into account their accuracy and the computing time. Both methods are employed for the analysis of the transmission of coupling constants through the hydrogen bond for ammonia clusters. A linear relation between the intermolecular constants ^1hJ_NH′ and the length of the hydrogen bond is found.     

Study of diffusion and local structure of sodium-silicate liquid: the molecular dynamic simulation

A systematic analysis on sodium-silicate melt with various silica contents was carried out. The simulation revealed two diffusion mechanisms occurred in the melt: the bond-breaking and hopping between sites. The local structure was analyzed through T-simplexes. It was revealed that T-clusters have a non-spherical shape and represent the diffusion channel, in which Na atoms are dominant, but no any O atoms are located. The SiO₂-poor melt acquires a long channel. In contrast, the SiO₂-rich melt consists of unconnected short channels. The simulation also revealed the immobile and mobile regions which differ in local structure and constituent composition. We propose a new CL-function to characterizing the spatial distribution of different atom component. The spatial distribution of mobile and immobile atoms is found quite different. In particular, the immobile atoms are concentrated in high-density regions possessing very large density of immobile atoms. The spatial distribution of mobile atoms in contrast is more homogeneous.     

Crystal and Molecular Structure of Dichloro(ethylenediamine)gold(III) Nitrate: [Au(NH<Subscript>2</Subscript>CH<Subscript>2</Subscript>CH<Subscript>2</Subscript>NH<Subscript>2</Subscript>)Cl<Subscript>2</Subscript>]NO<Subscript>3</Subscript>

Abstract  The gold(III) atom in [Au(NH₂CH₂CH₂NH₂)Cl₂]NO₃ is chelated by the ethylenediamine (en) ligand and the approximately square planar geometry is completed by two chloride atoms. Weak Au···O and Au···Cl contacts are noted above and below the square plane leading to a tetragonally distorted octahedron for the gold(III) center. Extensive charge-assisted hydrogen bonding of the type N–H···O leads to the formation of a 2-D array and layers are consolidated into a 3-D network via C–H···O and C–H···Cl contacts. The compound crystallizes in the orthorhombic space group Pbca with a = 10.3380(11) ?, b = 8.2105(7) ?, c = 19.625(2) ?, and Z = 8. Index Abstract  Square planar complex cations form additional Au···O and Au···Cl interactions to form a tetragonally distorted octahedron for gold. The ionic components are connected into a 2-D array via charge-assisted N–H···O hydrogen bonding interactions.