The Effect of Bonding on the Fragmentation of Small Systems

Recent dissociative recombination (DR) experiments have reported that the observed reaction products depend on the structure, bonding, and charge centre of the molecular ion. For examples, the dominant product channel observed in the DR of D5(+)(2), N2O2(+)(1), and D5O2(+)(3) suggests that the former two ions have the form D3(+) D2, and NO(+) NO(1), respectively, whilst the latter is known to have the form D2O D(+) D2O (3). Here we compare and contrast these observations by investigating the DR of one of the simplest such systems, Li(+) H2. This system, a weakly bound cluster with the charge centre located on the lithium atom, will provide us with an excellent opportunity for investigating the role played by the type of bonds and charge centre in the DR process

Enhanced cosmic-ray flux toward zeta Persei inferred from laboratory study of H3+ - e- recombination rate

The H3+ molecular ion plays a fundamental role in interstellar chemistry, as it initiates a network of chemical reactions that produce many interstellar molecules. In dense clouds, the H3+ abundance is understood using a simple chemical model, from which observations of H3+ yield valuable estimates of cloud path length, density, and temperature. On the other hand, observations of diffuse clouds have suggested that H3+ is considerably more abundant than expected from the chemical models. However, diffuse cloud models have been hampered by the uncertain values of three key parameters: the rate of H3+ destruction by electrons, the electron fraction, and the cosmic-ray ionisation rate. Here we report a direct experimental measurement of the H3+ destruction rate under nearly interstellar conditions. We also report the observation of H3+ in a diffuse cloud (towards zeta Persei) where the electron fraction is already known. Taken together, these results allow us to derive the value of the third uncertain model parameter: we find that the cosmic-ray ionisation rate in this sightline is forty times faster than previously assumed. If such a high cosmic-ray flux is indeed ubiquitous in diffuse clouds, the discrepancy between chemical models and the previous observations of H3+ can be resolved.Comment: 6 pages, Nature, in pres

Electron power absorption dynamics in capacitive radio frequency discharges driven by tailored voltage waveforms in CF4

The power absorption dynamics of electrons and the electrical asymmetry effect in capacitive radio-frequency plasmas operated in CF4 and driven by tailored voltage waveforms are investigated experimentally in combination with kinetic simulations. The driving voltage waveforms are generated as a superposition of multiple consecutive harmonics of the fundamental frequency of 13.56 MHz. Peaks/valleys and sawtooth waveforms are used to study the effects of amplitude and slope asymmetries of the driving voltage waveform on the electron dynamics and the generation of a DC self-bias in an electronegative plasma at different pressures. Compared to electropositive discharges, we observe strongly different effects and unique power absorption dynamics. At high pressures and high electronegativities, the discharge is found to operate in the drift-ambipolar (DA) heating mode. A dominant excitation/ionization maximum is observed during sheath collapse at the edge of the sheath which collapses fastest. High negative-ion densities are observed inside this sheath region, while electrons are confined for part of the RF period in a potential well formed by the ambipolar electric field at this sheath edge and the collapsed (floating potential) sheath at the electrode. For specific driving voltage waveforms, the plasma becomes divided spatially into two different halves of strongly different electronegativity. This asymmetry can be reversed electrically by inverting the driving waveform. For sawtooth waveforms, the discharge asymmetry and the sign of the DC self-bias are found to reverse as the pressure is increased, due to a transition of the electron heating mode from the α-mode to the DA-mode. These effects are interpreted with the aid of the simulation results

Dissociative recombination of the weakly bound NO-dimer cation: Cross sections and three-body dynamics

Contains fulltext : 32424.pdf (publisher's version ) (Open Access)Dissociative recombination (DR) of the dimer ion (NO)(2)(+) has been studied at the heavy-ion storage ring CRYRING at the Manne Siegbahn Laboratory, Stockholm. The experiments were aimed at determining details on the strongly enhanced thermal rate coefficient for the dimer, interpreting the dissociation dynamics of the dimer ion, and studying the degree of similarity to the behavior in the monomer. The DR rate reveals that the very large efficiency of the dimer rate with respect to the monomer is limited to electron energies below 0.2 eV. The fragmentation products reveal that the breakup into the three-body channel NO+O+N dominates with a probability of 0.69 +/- 0.02. The second most important channel yields NO+NO fragments with a probability of 0.23 +/- 0.03. Furthermore, the dominant three-body breakup yields electronic and vibrational ground-state products, NO(upsilon=0)+N(S-4)+O(P-3), in about 45% of the cases. The internal product-state distribution of the NO fragment shows a similarity with the product-state distribution as predicted by the Franck-Condon overlap between a NO moiety of the dimer ion and a free NO. The dissociation dynamics seem to be independent of the NO internal energy. Finally, the dissociation dynamics reveal a correlation between the kinetic energy of the NO fragment and the degree of conservation of linear momentum between the O and N product atoms. The observations support a mechanism in which the recoil takes place along one of the NO bonds in the dimer

Rotational state effects in the dissociative recombination of H2+

Contains fulltext : 36427.pdf (publisher's version ) (Open Access