Stark broadening and regularities of ionized neon and argon spectral lines

Stark widths of five Ne III, five Ne IV, one Ar III and nine ArIV spectral lines have been measured in a linear-pinch discharge plasma. The results were compared with existing experimental and theoretical results, and used to establish several types of regularities. Electron densities determined with single-wavelength laser interferometry were 2.18·10²³ m^?3 and 2.80·10²³ m^?3 in neon and argon plasma, respectively. The electron temperatures determined from the Boltzmann slope of several Ne III spectral lines, and ratios of Ne III to Ne IV or Ar III to Ar IV spectral lines were 59 000 K and 42 000 K in neon and argon plasma, respectively. The investigated spectral lines originate predominantly, from 3s–3p and 3s′–3p′ Ne III and Ne IV, and from 4s–4p and 4s′–4p′ Ar III and Ar IV transition arrays. The emphasis is on the Stark width (θ) dependence on the upper level ionization potential (I), the emitter core net charge (z) and electron temperature (T) for a given electron density. This dependence was found to be of the form: θ=az ² T ^?1/2 I ^?b , wherea andb are constants within(i) several stages of ionization of neon or argon and(ii) within nitrogen like (NI, O II, F III and Ne IV) 3s–3p or phosphorus like (P I, S II, Cl III and Ar IV) 4s–4p transition arrays. The established overall trends were used to predict the Stark widths of univestigated spectral lines originating from the given transition arrays.     

Stark broadening parameters of the 381.96 nm He I line

Stark width (W) and shift (d) of the neutral helium (He I) 381.96 nm spectral line in the high lying 2p-6d transition has been measured in the optically thin linear, low-pressure, pulsed arc discharge operated in the helium at 50 000 K electron temperature and 6.1 x 10²² m^-3 electron density. These values are the first experimentally obtained W and d related to this line. Unfortunately, comparison with theoretical results is not possible due to the fact that only one existing theoretical calculations has been done at a 10¹⁹ m^-3 electron density only. We have found negative line shift (toward the blue) that agree well with existing theoretical predictions.Received: 19 February 2004, Published online: 4 May 2004PACS: 52.70.Kz Optical (ultraviolet, visible, infrared) measurements - 32.70.Cs Oscillator strengths, lifetimes, transition moments - 32.70.-n Intensities and shapes of atomic spectral lines     

Bis-[3]Ferrocenophanes with Central >E−E’< Bonds (E,E’=P,SiH): Preparation,Properties, and Thermal Activation

A series of bis-[3]ferrocenophanes of the general type Fe(C₅H₄E’)₂E−E(E'C₅H₄)₂Fe (E=P, SiH and E’=PtBu, NneoPentyl, NSi(CH₃)₃) with an isolobal molecular framework have been prepared and characterized by heteronuclear NMR spectroscopy and X-ray crystallography. The thermal dissociation behavior with respect to homolytic fission of the central bond generating phosphorus centered radicals was investigated using EPR spectroscopy and quantum chemical calculations.     

On the line intensity ratios of prominent Si II,Si III,and Si IV multiplets

Line intensities of singly, doubly and triply ionized silicon (Si II, Si III, and Si IV, respectively) belonging to the prominent higher multiplets, are of interest in laboratory and astrophysical plasma diagnostics. We measured these line intensities in the emission spectra of pulsed helium discharge. The Si II line intensity ratios in the 3s3p²²D–3s²4p²P^o, 3s²3d²D–3s²4f²F^o, and 3s²4p²P^o–3s²4d²D transitions, the Si III line intensity ratios in the 3s3d³D–3s4p³P^o, 3s4p³P^o–3s4d³D, 3s4p³P^o–3s5s³S, 3s4s³S–3s4p³P^o, and 3s4f³F^o–3s5g³G transitions, and the Si IV line intensity ratios in the 4p²P^o–4d²D and 4p²P^o–5s²S transitions were obtained in a helium plasma at an electron temperature of about 17,000 ± 2000 K. Line shapes were recorded using a spectrograph and an ICCD camera as a highly-sensitive detection system. The silicon atoms were evaporated from a Pyrex discharge tube designed for the purpose. They represent impurities in the optically thin helium plasma at the silicon ionic wavelengths investigated. The line intensity ratios obtained were compared with those available in the literature, and with values calculated on the basis of available transition probabilities. The experimental data corresponded well with line intensity ratios calculated using the transition probabilities obtained from a Multi Configuration Hartree–Fock approximation for Si III and Si IV spectra. We recommend corrections of some Si II transition probabilities.     

Measured Cd III Stark widths

The Stark FWHM (Full-Width at Half of the Maximal line intensity, W) have been measured for 16 doubly ionized cadmium (Cd III) spectral lines in a pulsed helium discharge in the wavelength interval between 200 nm and 304 nm. The helium discharge was created in the linear low pressure pulsed arc operated at 19 000 K electron temperature and 5.0×¹⁰²² m−3 electron density. The cadmium atoms were sputtered from the cadmium (99.9% purity) cylindrical plates located in the linear part of the discharge tube. The high density of the Cd III ions is boosted by cascade ionization processes via the well populated Cd II energy levels due to the Penning and charge exchange effects. The shapes of the Cd III lines are recorded using a spectrograph (McPherson model 209, 1.33 m focal-length with 2400 grooves/mm holographic grating) and intensified CCD camera (Andor DH740-18F-03) as a high-sensitive detection system. The Stark parameters introduced in this Letter are the first published experimental Cd III Stark widths.     

Heteroannelated (+)-muricatacin mimics: synthesis, antiproliferative properties and structure-activity relationships

Six new (+)-muricatacin mimics bearing a furano-furanone core have been synthesized and their in vitro antiproliferative activity was evaluated against a panel of human tumour cell lines. A straightforward total synthesis of (+)-muricatacin (1) from d-xylose is disclosed providing a sample of 1 that served as a positive control in antitumour assays. All new compounds showed diverse antiproliferative effects against human malignant cell lines, but were devoid of any significant cytotoxicity towards the normal foetal lung fibroblasts (MRC-5). Additionally, the most of (+)-muricatacin analogues show selective cytotoxicities towards certain cancer cell lines, whereas only two of six analogues are broadly toxic against all cell lines under evaluation. A SAR study reveals the structural features that may be beneficial for the antiproliferative activity of these lactones. These include the absolute stereochemistry, introduction of a THF ring, interchange of the O₈ ether functionality and the C₈ methylene group in the side chain of muricatacin oxa analogues, as well as the one- or two-carbon homologation of the side chain in both 3 and 6.     

Palladium(II) complexes with R2edda-derived ligands. Part V. Reaction of O,O′-diethyl-(S,S)-ethylenediamine-N,N′-di-2-(3-methyl)butanoate with K2[PdCl4]

The reaction of K₂[PdCl₄] with [(S,S)-H₂(Et)₂eddv]Cl₂ diester (O,O′-diethyl-(S,S)-ethylenediamine-N,N′-di-2-(3-methyl)butanoate) (1) resulted in [PdCl₂{(S,S)-(Et)eddv-κ² N,N′,κO}] (2) complex with one hydrolyzed ester group. The compound was characterized by spectroscopic methods and it was found that the reaction is diastereoselective (¹H and ¹³C NMR; one diastereoisomer of four possible). In addition, the structure of 2 was confirmed by X-ray diffraction analysis, indicating that the product is the (R,R)–N,N′-configured isomer. DFT calculations support the formation of one diastereoisomer of 2.     

On the Cd III spectrum in a pulsed helium discharge

On the basis of the spectral line intensity relaxation during the plasma decay, fifty six spectral lines between 219 nm and 330 nm in the cadmium (Cd) spectrum were identified as Cd III (doubly ionized) or Cd IV (triply ionized) lines. The measured Stark widths of twelve, the most intense spectral lines around 315±15 nm with well defined profiles, are presented. Investigated spectral lines originate from the high lying energy levels, not classified up to now. A linear low-pressure pulsed arc was used as an optically thin plasma source. A pulsed discharge was produced in a pyrex discharge tube. Helium was chosen as the carrier gas. The cadmium atoms were sputtered from the thin cadmium cylindrical plates located in the homogeneous axial part of the discharge tube. The helium plasma was operated at electron temperatures up to 19 000 K and 1.1 × 10²³ m^-3 electron density. The stepwise ionization processes via the high lying singly ionized (Cd II) energy levels, populated well due to the Penning and charge exchange effects, provide high density of the Cd III (and Cd IV) ions in our helium plasma. The temporal evolutions of the spectral line intensities were monitored using a spectrograph and an ICCD camera as a highly sensitive detection system.     

A critical assessment of the specific role of microwave irradiation in the synthesis of ZnO micro- and nanostructured materials

A rapid, microwave-assisted hydrothermal method has been developed to access ultrafine ZnO hexagonal microrods of about 3-4 μm in length and 200-300 nm in width by using a 1:5 zinc nitrate/urea precursor system. The size and morphology of these ZnO materials can be influenced by subtle changes in precursor concentration, solvent system, and reaction temperature. Optimized conditions involve the use of a 1:3 water/ethylene glycol solvent system and 10 min microwave heating at 150 °C in a dedicated single-mode microwave reactor with internal temperature control. Carefully executed control experiments ensuring identical heating and cooling profiles, stirring rates, and reactor geometries have demonstrated that for these preparations of ZnO microrods no differences between conventional and microwave dielectric heating are observed. The resulting ZnO microrods exhibited the same crystal phase, primary crystallite size, shape, and size distribution regardless of the heating mode. Similar results were obtained for the ultrafast preparation of ZnO nanoparticles with diameters of approximately 20 nm, synthesized by means of a nonaqueous sol-gel process at 200 °C from a Zn(acac)(2) (acac=acetylacetonate) precursor in benzyl alcohol. The specific role of microwave irradiation in enhancing these nanomaterial syntheses can thus be attributed to a purely thermal effect as a result of higher reaction temperatures, more rapid heating, and a better control of process parameters.     

Two similar lactone-hydrochlorides with different types of hydrogen bonding networks: Crystal structure of (R,S)-α-amino-γ-caprolactone hydrochloride and racemic α-amino-γ-methyl-γ-valerolactone hydrochloride semihydrate

The X-ray crystal structure of (R,S)--amino--caprolactone hydrochloride (compound1) and -amino--methyl--valerolactone hydrochloride semihydrate (compound2) are presented. Both compound1 and compound2 belong to the orthorhombic system. Caprolactone-hydrochloride1 crystallizes in the space groupP2₁2₁2₁ witha=5.1948(7),b=8.7404(8),c=17.907(1) Å.V=813.0(2) ų,Z=4. Valerolactone-hydrochloride2 crystallizes in the space groupP na2₁ witha=26.771(8),b=5.1598(7),c=13.201(3) Å,V=1823.5(7) ų,Z=8. The lactone cations maintain the same, open envelope conformation in both crystals. The lactone-hydrochloride packing arrangements in1 and2 are distinctly different. While in1 N–H...Cl and N–H...O hydrogen bonding creates two dimensional nets in the form of puckered layers perpendicular to the [001] direction, in2 a water molecule of crystallization with an additional OW–H...Cl hydrogen interaction assists in forming a three-dimensional hydrogen-bond network throughout the crystal.