Experimental observation of dissociative electron attachment to S2O and S2O2 with a new spectrometer for unstable molecules

A new spectrometer, electron radical interaction chamber, has been developed to study dissociative electron attachment to unstable molecules such as free radicals. It includes a trochoidal electron monochromator and a time-of-flight mass spectrometer. Radicals are generated with a microwave discharge at 2.45 GHz. Preliminary data are presented for radicals formed when a mixture of helium and sulphur dioxide was passed through the microwave discharge. Several new resonances are observed with the discharge on. Resonances at 0 eV (S-), 0.8, 1.2, 3.0 eV (SO-) and 3.7 eV (SO- and S2O-) are assigned to the radical S2O2 and a resonance at 1.6 eV (S-) is assigned to S2O. No new resonances have been assigned to SO, which was also generated in the microwave discharge.

Virtual state scattering with cold electrons: para-xylene and para-difluorobenzene

The scattering of electrons with kinetic energies down to a few meV by para-xylene and para-difluorobenzene has been observed experimentally with an electron beam energy resolution of 0.95 to 1.5 meV (full width half maximum). At low electron energies the collisions can be considered as cold scattering events because the de Broglie wavelength of the electron is considerably larger than the target dimensions. The scattering cross sections measured rise rapidly at low energy due to virtual state scattering. The nature of this scattering process is discussed using s- and p-wave phase shifts derived from the experimental data. Scattering lengths are derived of, respectively, -9.5+/-0.5 and -8.0+/-0.5 a.u. for para-xylene and para-difluorobenzene. The virtual state effect is interpreted in terms of nuclear diabatic and partially adiabatic models, involving the electronic and vibronic symmetries of the unoccupied orbitals in the target species. The concept of direct and indirect virtual state scattering is introduced, through which the present species, in common with carbon dioxide and benzene, scatter through an indirect virtual state process, whereas other species, such as perfluorobenzene, scatter through a direct process. (C) 2005 American Institute of Physics.

Accurate computational methods for two-electron atom-laser interactions

We discuss the application of quantitatively accurate computational methods to the study of laser-driven two-electron atoms in short intense laser pulses. The fundamental importance of such calculations to the subject area is emphasized. Calculations of single- and double-electron ionization rates at 390 nm are presented. (C) 2001 Optical Society of America.

Analytical calculation of far infrared spectra of ice in terms of a molecular model

Wideband far infrared (FIR) spectra of complex permittivity e(p) of ice are calculated in terms of a simple analytical theory based on the method of dipolar autocorrelation functions. The molecular model represents a revision of the model recently presented for liquid water in Adv. Chem. Phys. 127 (2003) 65. A composite two-fractional model is proposed. The model is characterised by three phenomenological potential wells corresponding to the three FIR bands observed in ice. The first fraction comprises dipoles reorienting in a rather narrow and deep hat-like well; these dipoles generate the librational band centred at the frequency approximate to 880 cm(-1). The second fraction comprises elastically interacting particles; they generate two nearby bands placed around frequency 200 cm(-1). For description of one of these bands the harmonic oscillator (HO) model is used, in which translational oscillations of two charged molecules along the H-bond are considered. The other band is produced by the H-bond stretch, which governs hindered rotation of a rigid dipole. Such a motion and its dielectric response are described in terms of a new cut parabolic (CP) model applicable for any vibration amplitude. The composite hat-HO-CP model results in a smooth epsilon(nu) ice spectrum, which does not resemble the noise-like spectra of ice met in the known literature. The proposed theory satisfactorily agrees with the experimental ice spectrum measured at - 7 degrees C. The calculated longitudinal optic-transverse optic (LO-TO) splitting occurring at approximate to 250 cm(-1) qualitatively agrees with the measured data. (c) 2004 Elsevier B.V. All rights reserved.

Nonharmonic transverse vibration of the H-bonded molecules and the THz spectra in ice and water

A nonlinear equation of motion is found for the dimer comprising two charged H2O molecules. The THz dielectric response to nonharmonic vibration of a nonrigid dipole, forming the hydrogen bond (HB), is found in the direction transverse to this bond. An explicit expression is derived for the autocorrelator that governs the spectrum generated by transverse vibration (TV) of such a dipole. This expression is obtained by analytical solution of the truncated set of recurrence equations. The far infrared (FIR) spectra of ice at the temperature - 7 degrees C are calculated. The wideband, in the wavenumber (frequency) v range 0... 100.0 cm(-1), spectra are obtained for liquid water at room temperature and for supercooled water at -5.6 degrees C. All spectra are represented in terms of the complex permittivity epsilon(v) and the absorption coefficient alpha(v). The obtained analytical formula for epsilon comprises the term epsilon(perpendicular to) pertinent to the studied TV mechanism with three additional terms Delta epsilon(q), Delta epsilon(mu), and epsilon(or) arising, respectively, from: elastic harmonic vibration of charged molecules along the H-bond; elastic reorientation of HB permanent dipoles; and rather free libration of permanent dipoles in 'defects' of water/ice structure. The suggested TV-dielectric relaxation mechanism allows us: (a) to remove the THz 'deficit' of loss epsilon" inherent in previous theoretical studies; (b) to explain the THz loss and absorption spectra in supercooled (SC) water; and (c) to describe, in agreement with the experiment, the low- and high-frequency tails of the two bands of ice H2O located in the range 10...300 cm(-1). Specific THz dielectric properties of SC water are ascribed to association of water molecules, revealed in our study by transverse vibration of HB charged molecules. (C) 2006 Published by Elsevier B.V.

Changes in functional behavior of 93 % Pb(Mg1/3Nb2/3)O-3-7 % PbTiO3 thin films induced by ac electric fields

The dielectric properties of Au/[93%Pb(Mg1/3Nb2/3)O-3-7%PbTiO3] (PMN-PT)/(La0.5Sr0.5)CoO3/MgO thin-film capacitor heterostructures, made using pulsed laser deposition, have been investigated, with particular emphasis on the changes in response associated with increasing the magnitude of the ac measuring field. It was found that increasing the ac field caused a change in the frequency spectrum of relaxators, increasing the speed of response of "slow" relaxators, with an associated decrease in the freezing temperature (T-f) of the relaxor system; in addition, other characteristic parameters relating to polar relaxation (activation energy E-a and attempt frequency 1/tau(0)), described by fitting of the dielectric response to a Vogel-Fulcher expression, were found to change continuously as ac field levels were increased.

Charge exchange and dissociative processes in collisions of slow He2+ ions with H2O molecules

Experimental and theoretical studies of one-electron capture in collisions of He2+ ions with H2O molecules have been carried out in the range 0.025-12 keV amu(-1) corresponding to typical solar wind velocities of 70-1523 km s(-1). Translational energy spectroscopy (TES), photon emission spectroscopy (PES), and fragment ion spectroscopy were employed to identify and quantify the collision mechanisms involved. Cross sections for selective single electron capture into n=1, 2, and 3 states of the He+ ion were obtained using TES while PES provided cross sections for capture into the He+(2p) and He+(3p) states. Our model calculations show that He+(n=2) and He+(n=3) formation proceeds via a single-electron process governed by the nucleus-electron interaction. In contrast, the He+(1s) formation mechanism involves an exothermic two-electron process driven by the electron-electron interaction, where the potential energy released by the electron capture is used to remove a second electron thereby resulting in fragmentation of the H2O molecule. This process is found to become increasingly important as the collision energy decreases. The experimental cross sections are found to be in reasonable agreement with cross sections calculated using the Demkov and Landau-Zener models.

Negative photoion spectroscopy of freon molecules in the vicinity of the Cl 2p edge

Polar photodissociation of CFnCl4-n (n=0-2) has been studied using synchrotron radiation within the energy range 195-217 eV. The first observations of negative photoion fragments from these molecules after core excitation are reported. In addition to observing a number of previously known resonances two additional resonant states, just above the Cl 2p ionization limit, are observed and play an important role in the polar photodissociation process. The difficulties in identifying these above threshold spin-split features using negative photoion spectroscopy are discussed.

Molecular electrostatic properties of ions in an ionic liquid

We have analysed the electronic wave functions from an ab initio simulation of the ionic liquid (room temperature molten salt) dimethyl imidazolium chloride ([dmim][Cl] or [C1mim][Cl]) using localized Wannier orbitals. This allows us to assign electron density to individual ions. The probability distributions of the ionic dipole moments for an isolated ion and for ions in solution are compared. The liquid environment is found to polarize the cation by about 0.7 D and to increase the amplitude of the fluctuations in the dipole moments of both cation and anion. The relative changes in nuclear and electronic contributions are shown. The implications for classical force fields are discussed.

SOCS3 Targets Siglec 7 for Proteasomal Degradation and Blocks Siglec 7-mediated Responses

CD33-related Siglecs (sialic acid-binding immunoglobulin-like lectins) 5–11 are inhibitory receptors that contain a membrane proximal ITIM (immunoreceptor tyrosine-based inhibitory motif) (I/V/L/)XYXX(L/V), which can recruit SHP-1/2. However, little is known about the regulation of these receptors. SOCS3 (suppressor of cytokine signaling 3) is up-regulated during inflammation and competes with SHP-1/2 for binding to ITIM-like motifs on various cytokine receptors resulting in inhibition of signaling. We show that SOCS3 binds the phosphorylated ITIM of Siglec 7 and targets it for proteasomal-mediated degradation, suggesting that Siglec 7 is a novel SOCS target. Following ligation, the ECS E3 ligase is recruited by SOCS3 to target Siglec 7 for proteasomal degradation, and SOCS3 expression is decreased concomitantly. In addition, we found that SOCS3 expression blocks Siglec 7-mediated inhibition of cytokine-induced proliferation. This is the first time that a SOCS target has been reported to degrade simultaneously with the SOCS protein and that inhibitory receptors have been shown to be degraded in this way. This may be a mechanism by which the inflammatory response is potentiated during infection.

Dielectronic recombination of He-like to C-like iodine ions

KLL dielectronic recombination resonances, where a free electron is captured into the L shell and at the same time a K shell electron is excited into the L shell, have been measured for open shell iodine ions by measuring the detected yield of escaping ions of various charge states and modeling the charge balance in an electron beam ion trap. In the modeling, the escape from the trap and multiple charge exchange were considered. Extracted ions were used to measure the charge balance in the trap. The different charge states were clearly separated, which along with the correction for artifacts connected with ion escape and multiple charge exchange made the open shell highly charged ion measurements of this type possible for the first time. From the measured spectra resonant strengths were obtained. The results were 4.27(39)x10(-19) cm(2) eV, 2.91(26)x10(-19) cm(2) eV, 2.39(22)x10(-19) cm(2) eV, 1.49(14)x10(-19) cm(2) eV and 7.64(76)x10(-20) cm(2) eV for the iodine ions from He-like to C-like, respectively.