Radiative lifetimes in Ce I and Ce II

New radiative lifetime measurements based on time-resolved laser-induced fluorescence techniques are reported for 18 even-parity levels belonging to the 4f5d^26p and 4f ²5d ² configurations of Ce I and 6 even-parity levels belonging to the 5d^26s, 4f5d6p, and 4f6s6p configurations of Ce II. Free neutral and singly ionized cerium atoms were produced by laser ablation. The Ce I and Ce II levels range in energy from 26 545 to 29 102 cm^-1, and 42 573 to 48 152 cm^-1, respectively. Received 25 September 2002 Published online 4 March 2003     

Förster energy transfer from poly(arylene–ethynylene)s to an erbium–porphyrin complex

We study the infrared emission at 1.54 μm of an organolanthanide complex, Er(III)-tetraphenylporphyrin [Er(TPP)acac], both as a result of direct optical excitation and via energy transfer from host π-conjugate polymers of type poly(arylene–ethynylene) [PAE]. In the first case, the emission of the neat complex is characterized in inert transparent materials and a value of the quantum yield at 1.54 μm φ_IR=4×10⁻⁴ is measured. Then, fluorescence resonance transfer is investigated in blends of Er(TPP)acac with PAEs by monitoring the quenching of the polymer fluorescence along with the enhancement of both the visible emission of the ligand and the near-infrared band of Er³⁺. These different procedures allow a detailed analysis of the transfer efficiency within a specific implementation of the Förster model for polymeric donors. The experimental values of the critical radius R₀, ranging from 1.3 to 2.5 nm for the different blends, are in good agreement with theory for a wide interval of the physical and spectroscopic parameters. This suggests that other mechanisms for excitation transfer do not play a significant role in these materials.     

Ordered states and structural transitions in a system of Abrikosov vortices with periodic pinning

A system of Abrikosov vortices in a quasi-two-dimensional HTSC plate is considered for various periodic lattices of pinning centers. The magnetization and equilibrium configurations of the vortex density for various values of external magnetic field and temperature are calculated using the Monte Carlo method. It is found that the interaction of the vortex system with the periodic lattice of pinning centers leads to the formation of various ordered vortex states through which the vortex system passes upon an increase or a decrease in the magnetic field. It is shown that ordered vortex states, as well as magnetic field screening processes, are responsible for the emergence of clearly manifested peaks on the magnetization curves. Extended pinning centers and the effect of multiple trapping of vortices on the behavior of magnetization are considered. Melting and crystallization of the vortex system under the periodic pinning conditions are investigated. It is found that the vortex system can crystallize upon heating in the case of periodic pinning.     

Sulfobetaine‐containing diblock and triblock copolymers via reversible addition‐fragmentation chain transfer polymerization in aqueous media

A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by ¹H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003     

Evidences of phase separation in moisture‐cured poly(urethane urea)s by means of temperature modulated differential scanning calorimetry

The degree of phase separation in several moisture‐cured poly(urethane urea)s (PUUs) was studied by FTIR spectroscopy, wide angle X‐ray diffraction (WAXD), and temperature‐modulated differential scanning calorimetry (TMDSC). This latter technique was shown to be particularly useful in analysing the degree of phase separation in PUU polymers. Both phase mixing and phase segregation coexisted in the PUUs and the degree of phase separation increased as the urea hard segment (HS) content in the PUU increased. The maximum solubility of urea HSs into the polyol soft segments (SSs) was achieved for 50 wt % urea HS content in diol‐based PUUs, whereas for triol‐based PUUs the highest solubility between HS and SS was reached for lower urea HS amount. Finally, the higher the urea HS content the higher the extent of phase separation in the PUU. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3034–3045, 2007     

Spectral manifestations of distorted forms of Pd-porphin at helium temperatures: The effect of the matrix

The occurrence of two noninteracting forms of Pd-porphin in the ground electronic state in a wide number of Shpolskii matrices maintained at liquid helium temperature was observed with the help of the finestructure phosphorescence spectra of these systems. The ratio between these forms can be varied in wide limits by choosing a particular matrix, which indicates that the matrix plays a significant role in the conformation formation of the tetrapyrrole macrocycle. Based on comparison both with the resonance Raman spectra and with the results of investigations of metal complexes of porphin by the selective spectroscopy methods, the shortwavelength spectral form has been shown to correspond to the planar molecular structure, whereas the longwavelength form has been attributed to a nonplanar molecular structure with the distortion of the porphin macrocycle of the saddle type. The results obtained indicate that the methods of fine structure spectroscopy make it possible to efficiently study distorted molecular structures stabilized in solid matrices at low temperatures.     

Polarization dynamics of intracavity frequency-doubled Nd:YAG laser

Experimental study of low-frequency dynamics of an intracavity frequency-doubled Nd:YAG laser demonstrates the influence of the interaction of orthogonally polarized modes, participating in frequency doubling (type II phase matching), on the stability of the laser output. At a sufficiently low pump rate and low conversion efficiency, the laser shows stable operation with a low noise level at the frequencies of relaxation oscillations. At a high pump power and/or a high conversion efficiency, the laser emission becomes unstable as a result of Hopf bifurcation at the frequencies of relaxation oscillations that are responsible for the anti-phase polarization dynamics of the laser.     

What Oxidation State of Iron Determines the Amethyst Colour?

A colourless quartz crystal doped with ⁵⁷Fe³⁺ was obtained by hydrothermal synthesis in an NH₄F solution. The crystal was transformed into violet amethyst by gamma-irradiation. The change in colour was accompanied by changes in the Mössbauer spectrum that can be interpreted as the conversion of trivalent iron into the tetravalent state: Fe³⁺→Fe⁴⁺.

     

Lein?l, Lein?lfirniss und Oelfarben

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