Multi-pulse scheme for enhancing electron localization through vibrational wavepacket manipulation

A novel scheme for enhancing electron localization in intense-field dissociation is outlined. Through manipulation of a bound vibrational wavepacket in the exemplar deuterium molecular ion, simulations demonstrate that the application of multiple phase-locked, few-cycle IR pulses can provide a powerful scheme for directing the molecular dissociation pathway. By tuning the time delay and carrier–envelope–phase for a sequence of pulse interactions, the probability of the electron being localized to a chosen nucleus can be enhanced to above 80%.

Speciation of uranyl complexes in ionic liquids by optical spectroscopy

Uranyl complexes dissolved in room-temperature ionic liquids have diagnostic absorption and emission spectra which reflect the molecular symmetry and geometry. In particular, the characteristic vibrational fine structure of the absorption spectra allows identification of the molecular symmetry of a uranyl complex. The concept of speciation of. uranyl complexes is illustrated for the hydrated uranyl ion, the tetrachloro complex [UO2Cl4](2-), the trinitrato complex [UO2(NO3)(3)](-), the triacetato complex [UO2(CH3COO)(3)](-) and the crown ether complex [UO2(18-crown-6)](2+) in imidazolium and pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids. The competition between 18- crown-6 and small inorganic ligands for coordination to the uranyl ion was investigated. The crystal structures of the hydrolysis product [(UO2)(2)(mu(2)-OH)(2)(H2O)(6)] [UO2Br4](18-crown-6)(4) and imidazolium salt [C(6)mim](2)[UO2Br4] are described.

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.

Nebular and Auroral Emission Lines of [Ar IV] in the Optical Spectra of Planetary Nebulae

Recent R-matrix calculations of electron impact excitation rates in Ar IV are used to calculate the emission-line ratio: ratio diagrams (R₁, R₂), (R_1, R₃), and (R_1, R₄), where K₁ = I(4711 Å)/I(4740 Å), R₂ = I(7238 Å)/I(4711 + 4740 Å), R₃ = I(7263 Å)/I(4711 + 4740 Å), and R₄ = I(7171 Å)/I(4711 + 4740 Å), for a range of electron temperatures (T_e = 5000-20,000 K) and electron densities (N_e = 10-10⁶ cm^-3) appropriate to gaseous nebulae. These diagrams should, in principle, allow the simultaneous determination of T_e and N_e from measurements of the [Ar IV] lines in a spectrum. Plasma parameters deduced for a sample of planetary nebulae from (R_1, R₃) and (R_1, R₄), using observational date obtained with the Hamilton echelle spectrograph on the 3 m Shane Telescope at the Lick Observatory, are found to show excellent internal consistency and to be in generally good agreement with the values of T_e and N_e estimated from other line ratios in the echelle spectra. These results provide observational support for the accuracy of the theoretical ratios and, hence, the atomic data adopted in their derivation. In addition, they imply that the 7171 Å line is not as seriously affected by telluric absorption as previously thought. However, the observed values of R₂ are mostly larger than the theoretical high-temperature and density limit, which is due to blending of the Ar IV 7237.54 Å line with the strong C II transition at 7236 Å. 

Electron shell contributions to gamma-ray spectra of positron annihilation in noble gases

Gamma-ray positron annihilation spectra of the noble gases are simulated using computational chemistry tools for the bound electron wavefunctions and plane-wave approximation for the low-energy positron. The present annihilation line shapes, i.e. the full width at half maximum, Delta epsilon, of the gamma-ray annihilation spectra for He and Ar (valence) agree well with available independent atomic calculations using a different algorithm. For other noble gases they achieve moderate agreement with the experimental measurements. It is found that the contributions of various atomic electron shells to the spectra depend significantly on their principal quantum number n and orbital angular momentum quantum number l. The present study further reveals that the outermost ns electrons of the noble gases exhibit spectral line shapes in close agreement with those measured, indicating (as expected) that the measurements are not due to a simple sum over the momentum densities for all atomic electrons. The robust nature of the present approach makes it possible for us to proceed to more complex molecular systems using the tools of modern computational chemistry.

Many-body theory of gamma spectra from positron-atom annihilation

A many-body theory approach to the calculation of gamma spectra of positron annihilation on many-electron atoms is developed. We evaluate the first-order correlation correction to the annihilation vertex and perform numerical calculations for the noble gas atoms. Extrapolation with respect to the maximal orbital momentum of the intermediate electron and positron states is used to achieve convergence. The inclusion of correlation corrections improves agreement with experimental gamma spectra.

Comparison of positron-impact vibrational excitation cross sections with the Born-dipole model

The development of cold trap-based positron beams and new scattering techniques has recently enabled the ?rst measurements of state-resolved positron-impact vibrational excitation cross sections. These measurements revealed a number of features worth further consideration, such as relatively sharp increases near threshold. This paper describes a comparison of the magnitudes and shapes of these cross sections with the predictions of the Born-dipole model. Agreement of the magnitudes of the cross sections varies widely, ranging from reasonable to excellent agreement for CO2 and CF4 to poor agreement for CO and CH4. In contrast, the energy dependence of these cross sections in all these cases is close to that predicted by the Born model.

Positron-molecule interactions: Resonant attachment, annihilation, and bound states

This article presents an overview of current understanding of the interaction of low-energy positrons with molecules with emphasis on resonances, positron attachment, and annihilation. Measurements of annihilation rates resolved as a function of positron energy reveal the presence of vibrational Feshbach resonances (VFRs) for many polyatomic molecules. These resonances lead to strong enhancement of the annihilation rates. They also provide evidence that positrons bind to many molecular species. A quantitative theory of VFR-mediated attachment to small molecules is presented. It is tested successfully for selected molecule (e.g., methyl halides and methanol) where all modes couple to the positron continuum. Combination and overtone resonances are observed and their role is elucidated. Molecules that do not bind positrons and hence do not exhibit such resonances are discussed. In larger molecules, annihilation rates from VFR far exceed those explicable on the basis of single-mode resonances. These enhancements increase rapidly with the number of vibrational degrees of freedom, approximately as the fourth power of the number of atoms in the molecule. While the details are as yet unclear, intramolecular vibrational energy redistributio (IVR) to states that do not couple directly to the positron continuum appears to be responsible for these enhanced annihilation rates. In connection with IVR, experimental evidence indicates that inelastic positron escape channels are relatively rare. Downshifts of the VFR from the vibrational mode energies, obtained by measuring annihilate rates as a function of incident positron energy, have provided binding energies for 30 species. Their dependence upon molecular parameters and their relationship to positron-atom and positron-molecule binding-energy calculations are discussed. Feshbach resonances and positron binding to molecules are compared with the analogous electron-molecul (negative-ion) cases. The relationship of VFR-mediated annihilation to other phenomena such as Doppler broadening of the gamma-ray annihilation spectra, annihilation of thermalized positrons in gases, and annihilation-induced fragmentation of molecules is discussed. Possible areas for future theoretical and experimental investigation are also discussed.