Nebular and auroral emission lines of [Cl III] in the optical spectra of planetary nebulae

Electron impact excitation rates in Cl III, recently determined with the R-matrix code, are used to calculate electron temperature (T-e) and density (N-e) emission line ratios involving both the nebular (5517.7, 5537.9 Angstrom) and auroral (8433.9, 8480.9, 8500.0 Angstrom) transitions. A comparison of these results with observational data for a sample of planetary nebulae, obtained with the Hamilton Echelle Spectrograph on the 3-m Shane Telescope, reveals that the R-1 = /(5518 Angstrom)/I(5538 Angstrom) intensity ratio provides estimates of N-e in excellent agreement with the values derived from other line ratios in the echelle spectra. This agreement indicates that R-1 is a reliable density diagnostic for planetary nebulae, and it also provides observational support for the accuracy of the atomic data adopted in the line ratio calculations. However the [Cl III] 8433.9 Angstrom line is found to be frequently blended with a weak telluric emission feature, although in those instances when the [Cl III] intensity may be reliably measured, it provides accurate determinations of T-e when ratioed against the sum of the 5518 and 5538 Angstrom line fluxes. Similarly, the 8500.0 Angstrom line, previously believed to be free of contamination by the Earth's atmosphere, is also shown to be generally blended with a weak telluric emission feature. The [CI III] transition at 8480.9 Angstrom is found to be blended with the He I 8480.7 Angstrom line, except in planetary nebulae that show a relatively weak He I spectrum, where it also provides reliable estimates of T-e when ratioed against the nebular lines. Finally, the diagnostic potential of the near-UV [Cl III] lines at 3344 and 3354 Angstrom is briefly discussed.

Many-body theory calculations of positron binding to negative ions

A many-body theory approach developed by the authors [Phys. Rev. A 70, 032720 (2004)] is applied to positron bound states and annihilation rates in atomic systems. Within the formalism, full account of virtual positronium (Ps) formation is made by summing the electron-positron ladder diagram series, thus enabling the theory to include all important many-body correlation effects in the positron problem. Numerical calculations have been performed for positron bound states with the hydrogen and halogen negative ions, also known as Ps hydride and Ps halides. The Ps binding energies of 1.118, 2.718, 2.245, 1.873 and 1.393 eV and annihilation rates of 2.544, 2.482, 1.984, 1.913 and 1.809 ns^{-1}, have been obtained for PsH, PsF, PsCl, PsBr and PsI, respectively.

Large-scale density functional calculations of the surface properties of the Wigner crystal

The surface properties of the jellium model have been investigated by large supercell computations in the density functional theory-local spin-density (DFT-LSD) approach for planar slabs with up to 1000 electrons. A wide interval of densities has been explored, extending into the stability range of the Wigner crystal. Most computations have been carried out on nominally paramagnetic samples with an equal number of spin-up and spin-down electrons. The results show that within DFT-LSD spontaneous spin polarization and charge localization start nearly simultaneously at the surface for r(s) similar to 20, then, with decreasing density, they progress toward the center of the slab. Electrons are fully localized and spin polarized at r(s) = 30. At this density the charge distribution is the superposition of disjoint charge blobs, each corresponding to one electron. The distribution of blobs displays both regularities and disorder, the first being represented by well-defined planes and simple in-plane geometries, and the latter by a variety of surface defects. The surface energy, surface dipole, electric polarisability, and magnetization pattern have been determined as a function of density. All these quantities display characteristic anomalies at the density of the localization transition. The analysis of the low-frequency electric conductivity shows that in the fluid paramagnetic regime the in-plane current preferentially flows in the central region of the slab and the two spin channels are equally conducting. In the charge localized, spin-polarized regime, conductivity is primarily a surface effect, and an apparent asymmetry is observed in the two spin currents.

An understanding of chemoselective hydrogenation on crotonaldehyde over Pt(111) in the free energy landscape: The microkinetics study based on first-principles calculations

Microkinetic model is developed in the free energy landscape based on density functional theory (DFT) to quantitatively investigate the reaction mechanism of chemoselective partial hydrogenation of crotonaldehyde to crotyl alcohol over Pt(1 1 1) at the temperature of 353 K. Three different methods (mobile, immobile and collision theory models) were carried out to obtain free energy barrier of adsorption/desorption processes. The results from mobile and collision theory models are similar. The calculated TOFs from both models are close to the experiment value. However, for the immobile model, in which the free energy barrier of desorption approaches the energy barrier, the calculated TOF is 2 orders of magnitude lower than the other models. The difficulty of adsorption/ desorption may be overestimated in the immobile model. In addition, detailed analyses show that for the surface hydrogenation elementary steps, the entropy and internal energy effects are small under the reaction condition, while the zero-point-energy (ZPE) correction is significant, especially for the multi-step hydrogenation reaction. The total energy with the ZPE correction approaches to the full free energy calculation for the surface reaction under the reaction condition. (c) 2011 Elsevier B.V. All rights reserved.

Effect of alkali on methylene blue (CI Basic Blue 9) and other thiazine dyes

A detailed study of the action of alkali on methylene blue (Cl. Basic Blue 9) and other thiazine dyes was carried out through a combination of UV/visible spectroscopy, thin layer chromatography, mass and NMR spectrometry and computational methods. In 0.1 M aq alkali solution, methylene blue forms a highly coloured, lipophilic species that is mainly Bernthsen's methylene violet i.e. a hydrolysis decomposition product, this being contrary to the report of a red N-hydroxy methylene blue adduct. The nature of the heterocyclic nitrogen atom in C.I. Basic Blue 9 is discussed and it is concluded there is no basis for the proposal of nucleophile addition at this site of the dye. In contrast, other thiazine dyes are deprotonated by alkali to form their neutral, highly coloured, lipophilic conjugate base forms. (C) 2010 Elsevier Ltd. All rights reserved.

Calculations for doubly-excited states populated in two-electron processes

Recent calculations of doubly-excited states for two and four-electron states in neutral atoms and ions are described. In particular the radiative properties of these states are considered. It is pointed out that some of these states live so long that triply-excited states perhaps can be formed in neutralisation processes at surfaces. © 1991 Springer-Verlag.

yambo: An ab initio tool for excited state calculations

yambo is an ab initio code for calculating quasiparticle energies and optical properties of electronic systems within the framework of many-body perturbation theory and time-dependent density functional theory. Quasiparticle energies are calculated within the GW approximation for the self-energy. Optical properties are evaluated either by solving the Bethe-Salpeter equation or by using the adiabatic local density approximation. yambo is a plane-wave code that, although particularly suited for calculations of periodic bulk systems, has been applied to a large variety of physical systems. yambo relies on efficient numerical techniques devised to treat systems with reduced dimensionality, or with a large number of degrees of freedom. The code has a user-friendly command-line based interface, flexible 110 procedures and is interfaced to several publicly available density functional ground-state codes.