Relativistic four-component calculations of Buckingham birefringence using London atomic orbitals

We present the first relativistic study of the electric-field-gradient induced birefringence (Buckingham birefringence), with application to the series of molecules CX₂ (X?=?O, S, Se, Te). A recently developed atomic-orbital-driven scheme for the calculation of time-dependent molecular properties using one-, two- and four-component relativistic wave functions (Bast et?al. in Chem Phys 356:177, 2009) is extended to first-order frequency-dependent magnetic-field perturbations, using London atomic orbitals to ensure gauge-origin independent results and to improve basis-set convergence. Calculations are presented at the Hartree?CFock and Kohn?CSham levels of theory and results for CO₂ and CS₂ are compared with previous high-level coupled-cluster calculations. Except for the heaviest member of the series, relativistic effects are small??in particular for the temperature-independent contribution to the birefringence. By contrast, the effects of electron correlation are significant. However, the reliability of standard exchange-correlation functionals in describing Buckingham birefringence remains unclear based on the comparison with high-level coupled-cluster singles-and-doubles calculations.     

K3TaF8 from laboratory X‐ray powder data

The crystal structure of tripotassium octafluoridotantalate, K₃TaF₈, determined from laboratory powder diffraction data by the simulated annealing method and refined by total energy minimization in the solid state, is built from discrete potassium cations, fluoride anions and monocapped trigonal–prismatic [TaF₇]²⁻ ions. All six atoms in the asymmetric unit are in special positions of the P6₃mc space group: the Ta and one F atom in the 2b (3m) sites, the K and two F atoms in the 6c (m) sites, and one F atom in the 2a (3m) site. The structure consists of face‐sharing K₆ octahedra with a fluoride anion at the center of each octahedron, forming chains of composition [FK₃]²⁺ running along [001] with isolated [TaF₇]²⁻ trigonal prisms in between. The structure of the title compound is different from the reported structure of Na₃TaF₈ and represents a new structure type.     

Thermoanalytical study of water-based aluminium rolling fluids combined with direct observation

During cold-rolling of aluminium sheets the auxiliary lubricant fluids used decompose giving rise to discolouring of the sheet surface. In the present study a combined TGA-DTG-DTA analysis has been used in combination with direct observation of the colour change of carboxylate-based fluids in oxidizing and inert atmosphere to determine the temperature region of decomposition and/or polymerization. Significant effects have been observed depending not only on the type of atmosphere but also on the type of the cationic part of the organic component in these fluids.     

Pulsed ytterbium-doped large mode area double-clad fiber amplifier in MOFPA configuration

A pulsed master oscillator fiber power amplifier working in nanosecond range has been developed. An ytterbium-doped double-clad (large mode area) optical fiber was used as an amplifying medium. Actively Q-switched Nd:YVO laser was used as a seed of light pulses. The system worked at the repetition rate from 10 kHz to 40 kHz. At the amplifier output, pulses of 10.9 kW peak-power were achieved. The laser system worked at the slope efficiency of 30%.     

Tl2Te and its relationship with Tl5Te3

The crystal structure of Tl₂Te, dithallium telluride, has been determined by single‐crystal X‐ray diffraction. The analysis of the structure shows that this compound is the first known representative of a new crystal structure type. The structural relationship with the related Tl₅Te₃ phase is discussed.     

100 GW pulsed iodine photodissociation laser system PERUN I

The photodissociation iodine laser system PERUN I is described. The laser generates and amplifies the subnanosecond pulse with the energy about 80 J of the fundamental wavelength 1·315 μm and beam diameter 10 cm. The physical principles of this type of the high power laser are briefly explained and the laser system and its characteristics are described from the physical and technical point of view. Special attention is paid to the realization of such system with the slow optical pumping (≈300 μs).     

Catalytic enantioselective conjugate addition of dialkylzinc reagents to N-substituted-2,3-dehydro-4-piperidones

The first, highly enantioselective, copper/phosphoramidite-catalyzed conjugate addition of dialkylzinc reagents to N-substituted 2,3-dehydro-4-piperidones is described.