INFLUENCE OF CORE POLARIZATION ON THE ELECTRON-AFFINITY OF CA

We have developed a method, based on the use of B-spline basis sets and model potentials, for determining properties of systems with two or three electrons outside a polarizable closed-shell core. It is applied to the calculation of the electron affinity of Ca and the resulting value of 17.7 meV is in excellent agreement with the most recent experiments. It is found that the dielectronic core-valence interaction reduces the electron affinity by 39.5 meV.

Dissociative electron attachment to HCCCN

Dissociative electron attachment to cyanoacetylene (propiolonitrile) HCCCN has been observed in the electron energy range 0-12 eV. Negative ions are formed in two main bands with maxima at similar to 1.6 eV (CCCN-) and similar to 5.3 eV (CCCN-, CN-, HCC- and CC-). There are also weaker resonances which lead to dissociative electron attachment to form CN-, HCC- and CC- with a maximum intensity at similar to 8.1 eV and CCCN-, CN- and CC- at similar to 11.2 eV. A trace of CCN- is observed at similar to 9.1 eV. The positions of the main dissociative attachment bands observed are close to positions of pi* resonances recently calculated by Sommerfeld and Knecht. Calculations have also been performed in this work, which confirm the position of the p* orbitals. The electron affinity of the CCCN radical is determined as 4.59 +/- 0.25 eV from the threshold for CCCN- formation at 1.32 +/- 0.15 eV. Dissociative electron attachment to this molecule will act as a source of negative ions in extraterrestrial environments where electrons are present with more than 1.3 eV energy.

Excess electron interactions with solvated DNA nucleotides:Strand breaks possible at room temperature

When biological matter is subjected to ionizing radiation, a wealth of secondary low-energy (<20 eV) electrons are produced. These electrons propagate inelastically, losing energy to the medium until they reach energies low enough to localize in regions of high electron affinity. We have recently shown that in fully solvated DNA fragments, nucleobases are particularly attractive for such excess electrons. The next question is what is their longer-term effect on DNA. It has been advocated that they can lead to strand breaks by cleavage of the phosphodiester C-3'-O-3' bond. Here we present a first-principles study of free energy barriers for the cleavage of this bond in fully solvated nucleotides. We have found that except for dAMP, the barriers are on the order of 6 kcal/mol, suggesting that bond cleavage is a regular feature at 300 K. Such low barriers are possible only as a result of solvent and thermal fluctuations. These findings support the notion that low-energy electrons can indeed lead to strand breaks in DNA.

Enrichment and analysis of nonenzymatically glycated peptides: Boronate affinity chromatography coupled with electron-transfer dissociation mass spectrometry

Nonenzymatic glycation of peptides and proteins by D-glucose has important implications in the pathogenesis of diabetes mellitus, particularly in the development of diabetic complications. However, no effective high-throughput methods exist for identifying proteins containing this low-abundance posttranslational modification in bottom-up proteomic studies. In this report, phenylboronate affinity chromatography was used in a two-step enrichment scheme to selectively isolate first glycated proteins and then glycated, tryptic peptides from human serum glycated in vitro. Enriched peptides were subsequently analyzed by alternating electron-transfer dissociation (ETD) and collision induced dissociation ( CID) tandem mass spectrometry. ETD fragmentation mode permitted identification of a significantly higher number of glycated peptides (87.6% of all identified peptides) versus CID mode (17.0% of all identified peptides), when utilizing enrichment on first the protein and then the peptide level. This study illustrates that phenylboronate affinity chromatography coupled with LC-MS/MS and using ETD as the fragmentation mode is an efficient approach for analysis of glycated proteins and may have broad application in studies of diabetes mellitus.

Electron attachment to SF(6) and lifetimes of SF(6)(-) negative ions

We study the process of low-energy electron capture by the SF(6) molecule. Our approach is based on the model of Gauyacq and Herzenberg [J. P. Gauyacq and A. Herzenberg, J. Phys. B 17, 1155 (1984)] in which the electron motion is coupled to the fully symmetric vibrational mode through a weakly bound or virtual s state. By tuning the two free parameters of the model, we achieve an accurate description of the measured electron attachment cross section and good agreement with vibrational excitation cross sections of the fully symmetric mode. An extension of the model provides a limit on the characteristic time of intramolecular vibrational relaxation in highly excited SF(6)(-). By evaluating the total vibrational spectrum density of SF(6)(-), we estimate the widths of the vibrational Feshbach resonances of the long-lived negative ion. We also analyze the possible distribution of the widths and its effect on the lifetime measurements, and investigate nonexponential decay features in metastable SF(6)(-).

Electron detachment from negative ions in a short laser pulse

We present an efficient and accurate method to study electron detachment from negative ions by a few-cycle linearly polarized laser pulse. The adiabatic saddle-point method of Gribakin and Kuchiev [Phys. Rev. A 55, 3760 (1997)] is adapted to calculate the transition amplitude for a short laser pulse. Its application to a pulse with N optical cycles produces 2(N + 1) saddle points in complex time, which form a characteristic "smile." Numerical calculations are performed for H(-) in a 5-cycle pulse with frequency 0.0043 a.u. and intensities of 10(10), 5 x 10(10), and 10(11) W/cm(2), and for various carrier-envelope phases. We determine the spectrum of the photoelectrons as a function of both energy and emission angle, as well as the angle-integrated energy spectra and total detachment probabilities. Our calculations show that the dominant contribution to the transition amplitude is given by 5-6 central saddle points, which correspond to the strongest part of the pulse. We examine the dependence of the photoelectron angular distributions on the carrier-envelope phase and show that measuring such distributions can provide a way of determining this phase.

Dissociative electron attachment to the highly reactive difluoromethylene molecule–importance of CF2 for negative ion formation in fluorocarbon plasmas

Dissociative electron attachment to the highly reactive difluoromethylene molecule, CF2, produced in a C3F6/He microwave plasma and stepwise via the fast atom reaction CF3I+H?CF3+HI and CF3+H?CF2+HF, has been investigated. The upper limit for the cross section of formation of F- via dissociative electron attachment to CF2 is estimated to be 5×10-4?Å2. This value is four orders of magnitude smaller than the cross section previously predicted from scattering calculations. It is concluded that difluoromethylene plays a negligible role in negative ion formation in fluorocarbon plasmas.

ELECTRON-ENERGY DISTRIBUTION-FUNCTIONS AND NEGATIVE-ION CONCENTRATIONS IN TANDEM AND HYBRID MULTICUSP NEGATIVE HYDROGEN-ION SOURCES

The second derivative of a Langmuir probe characteristic is used to establish the electron energy distribution function (EEDF) in both a tandem and hybrid multicusp H- ion source. Moveable probes are used to establish the spatial variation of the EEDF. The negative ion density is measured by laser induced photo-detachment. In the case of the hybrid source the EEDF consists of a cold Maxwellian in the central region of the source; the electron temperature increases with increasing discharge current (rising from 0.3 eV at 1 A to 1.2 eV at 50 A when the pressure is 0.4 Pa). A hot-electron tail exists in the EEDF of the driver region adjacent to each filament which is shown to consist of a distinct group of primary electrons at low pressure (0.08 Pa) but becomes degraded mainly through inelastic collisions at higher pressures (0.27 Pa). The tandem source, on the other hand, has a single driver region which extends throughout the central region. The primary electron confinement times are much longer so that even at the lowest pressure considered (0.07 Pa) the primaries are degraded. In both cases the measured EEDF at specific locations and values of discharge operating parameters are used to establish the rate coefficients for the processes of importance in H- production and destruction.

Vibrational excitation of the N2+ first negative (0,0), (1,0) and (2,0) bands by electron impact: a theoretical study using the R-matrix approach

Ab initio cross section calculations for vibronic excitation using the R -matrix approach have been performed on the N 2 + molecular ion complex. A three-state close-coupling expansion is used where the electronic target states; X 2 g + , A 2 u and B 2 u + of the molecular cation are represented by a valence configuration-interaction approximation. A non-adiabatic approximation is invoked to study vibronic excitation for the first three negative bands, (0,0), (1,0) and (2,0) of the X-B transition (B 2 u + v ´ X 2 g + v ´´ ) of N 2 + . Fixed-nuclei and non-adiabatic cross section results are compared with the available experimental data for the (0,0) band and the breakdown of the adiabatic fixed-nuclei approximation is clearly evident for the vibronic excitation of the (1,0) and (2,0) bands in this molecular ion complex.

Capture and loss of electron by MeV ions penetrating through liquid spray:Formation of negative ion and neutral atom beams

Charge changing processes of MeV ions penetrating through liquid spray is confirmed to be abundant source of various energetic negative ion and neutral atom beams its generic nature is demonstrated.

Double ionization of atomic negative ions in an intense laser field

In recent years there have been many studies of multiple ionization of closed shell rare gas atoms by intense laser fields. Until now no similar work has been done in the study of more diverse targets such as negative ions where low binding energies and strong electron correlations could yield distinctive behaviour. We present the first results of ionization of more than one electron from a range of atomic negative ions by intense laser pulses. Although these pulses are long by modern standards, and tend to produce sequential ionization in atoms, the positive ion yields from the negative ions do not depend predictably on the ionization potentials. This suggests that there may, intriguingly, be an alternative mechanism enhancing double ionization at low intensities.

Energy dependence for pair production with electron capture in relativistic heavy-ion collisions

In 'Charge transfer from the negative-energy continuum: alternative mechanism for pair production in relativistic atomic collisions', Eichler (1995 Phys. Rev. Lett. 75 3653) proposes an alternative mechanism for capture by pair production, and from it derives an analytic expression for the total cross section with a surprisingly strong energy dependence. We show that, in fact, there is no alternative mechanism; rather the above mechanism may be more transparently viewed as an ionization-like transition in one centre with inclusion of continuum distortion by the second centre. We further show that to Centre the initial and final states on the target and projectile leads to confusion in the momentum transfer vectors, and hence, respectively that the alleged high-energy behaviour is erroneous.

Evidence for rescattering in intense, femtosecond laser interactions with a negative ion

It is now well established that energetic electron emission, nonsequential ionization, and high harmonic generation, produced during the interaction of intense, femtosecond laser pulses with atoms (and atomic positive ions), can be explained by invoking rescattering of the active electron in the laser field, the so-called rescattering mechanism. In contrast for negative ions, the role of rescattering has not been established experimentally. By irradiating F- ions with ultrashort laser pulses, F+ ion yields as a function of intensity for both linearly and circularly polarized light have been measured. We find that, at intensities well below saturation for F+ production by sequential ionization, there is a small but significant enhancement in the yield for the case of linearly polarized light, providing the first clear experimental evidence for the existence of the rescattering mechanism in negative ions.

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.