Low divergence cold-wall oven for loading ion traps.

We present a compact cold-wall oven that is simple to build and align for loading miniature ion traps with calcium ions. The cold-wall oven, which is a metal-loaded capillary heated only through a portion of its length by the passage of a current, is described and characterized. An atomic beam with a low divergence of 14 mrad is produced. We perform Doppler-sensitive, resonant fluorescence measurements on the atomic beam to characterize the oven's performance. The emission of atoms from the oven is seen within ∼70 s after turning on the oven at an electric power consumption of <10 W. The flow rate is measured to be 1.5 ± 0.2 × 109 atoms s-1 at a temperature of 702 ± 7 K. The entire oven assembly is mounted on a CF16 feedthrough. This design can be extended to other species for producing a collimated atomic beam.

Origin of Resonant Character in the Electron Impact Two-Body Neutral-Fragmentation of Methane.

The observation of peaks in the threshold region of two-body neutral fragmentation of methane molecule, i. e., CH4 →CH3 +H, by low energy electron (LEE) impact has been an enigma. The prevailing explanation that this resonant behavior is due to excitation energy transfer is unsatisfactory since this process is not expected to show peaks in the cross-sections unless there is the involvement of electron-molecule resonances. Our first-principles calculations now reveal that the observed peaks could be explained as due to the formation of negative ion resonances, which dominantly dissociate into two neutral fragments and a free-electron. This case of methane is a pointer to the possibility that such reactions contribute significantly to neutral radical production from molecules by LEE impact in comparison to dissociative electron attachment, and in general could play a significant role in electron-based chemical control.

DEA dynamics of chlorine dioxide probed by velocity slice imaging.

We report, for the first time, the detailed dynamics of dissociative electron attachment to the atmospherically important chlorine dioxide (OClO) molecule exploring all the product anion channels. Below 2 eV, the production of vibrationally excited OCl- dominates the DEA process whereas at electron energies greater than 2 eV, three-body dissociation is found to result in O- and Cl- production. We find that the internal energy of OCl- and the kinetic energy of Cl- are large enough for them to be relevant in the ozone-depleting catalytic cycle and more investigations on the reaction of these anions with ozone are necessary to completely understand the role of DEA to OClO in ozone depletion. These results also point to an urgent need for comprehensive theoretical calculations of the DEA process to this atmospherically important molecule.

Formation of CO2 from formic acid through catalytic electron channel.

Low energy electrons can initiate and control chemical reactions through resonant attachment forming an electron-molecule compound state. Recently, it has been theoretically shown that free electrons can also act as catalysts in chemical reactions. We investigate this novel concept for the case of conversion of formic acid into CO2. Resonant production of CO2 from cold formic acid films by low energy electron impact is observed using Fourier transform infrared spectroscopy. The resonant peak observed at 6 eV is identified as the catalytic electron channel. The experimental results are augmented with the ab initio quantum chemical calculations.

Electron induced reactions in condensed mixtures of methane and ammonia.

We demonstrate the efficient formation of carbon-nitrogen bonds starting from CH4 and NH3 on a metal surface at cryogenic temperatures. Electrons in the energy range of 1-90 eV are used to initiate chemical reactions in mixed molecular films of CH4 and NH3 at ∼15 K, and the products are detected by performing temperature programmed desorption (TPD). Extensive dehydrogenation occurs at all energies giving the products CH2NH and HCN in preference to CH3NH2. This is likely to do with the energetics of the reactions and the subsequent stability of these species in the condensed film. Thermal processing of the irradiated mixture favours dehydrogenation as indicated by the results of using different desorption rates. Electron impact excitation and subsequent dissociation into radicals is the reaction-initiating step rather than ionization of CH4 and NH3, as inferred from the yield of products as a function of electron energy. This could give insight into the important catalytic process of the industrial scale synthesis of HCN from CH4 and NH3 over Pt. This may also be a relevant pathway in the astrochemical environment where CN and HCN are abundant and low-energy electrons are found ubiquitously.

Dissociation dynamics of transient anion formed via electron attachment to sulfur dioxide.

We report the molecular dynamics of dissociative electron attachment to sulfur dioxide (SO2) by measuring the momentum distribution of fragment anions using the velocity slice imaging technique in the electron energy range of 2-10 eV. The S- channel results from symmetric dissociation which exhibits competition between the stretch mode and bending mode of vibration in the excited parent anion. The asymmetric dissociation of parent anions leads to the production of O- and SO- channels where the corresponding neutral fragments are formed in their ground as well as excited electronic states. We also identify that internal excitation of SO- is responsible for its low yield at higher electron energies.

Communication: Electron ionization of DNA bases.

No reliable experimental data exist for the partial and total electron ionization cross sections for DNA bases, which are very crucial for modeling radiation damage in genetic material of living cell. We have measured a complete set of absolute partial electron ionization cross sections up to 500 eV for DNA bases for the first time by using the relative flow technique. These partial cross sections are summed to obtain total ion cross sections for all the four bases and are compared with the existing theoretical calculations and the only set of measured absolute cross sections. Our measurements clearly resolve the existing discrepancy between the theoretical and experimental results, thereby providing for the first time reliable numbers for partial and total ion cross sections for these molecules. The results on fragmentation analysis of adenine supports the theory of its formation in space.

Serial bronchoscopic lung lavage in pulmonary alveolar proteinosis under local anesthesia.

Pulmonary alveolar proteinosis (PAP) is a rare disease, characterized by alveolar accumulation of surfactant composed of proteins and lipids due to defective surfactant clearance by alveolar macrophages. Mainstay of treatment is whole lung lavage, which requires general anesthesia. Herein, we report a case of primary PAP, successfully treated with serial bronchoscopic lung lavages under local anesthesia.

Dissociative electron attachment studies on acetone.

Dissociative electron attachment (DEA) to acetone is studied in terms of the absolute cross section for various fragment channels in the electron energy range of 0-20 eV. H(-) is found to be the most dominant fragment followed by O(-) and OH(-) with only one resonance peak between 8 and 9 eV. The DEA dynamics is studied by measuring the angular distribution and kinetic energy distribution of fragment anions using Velocity Slice Imaging technique. The kinetic energy and angular distribution of H(-) and O(-) fragments suggest a many body break-up for the lone resonance observed. The ab initio calculations show that electron is captured in the multi-centered anti-bonding molecular orbital which would lead to a many body break-up of the resonance.

State selectivity and dynamics in dissociative electron attachment to CF3I revealed through velocity slice imaging.

In light of its substantially more environmentally friendly nature, CF3I is currently being considered as a replacement for the highly potent global-warming gas CF4, which is used extensively in plasma processing. In this context, we have studied the electron-driven dissociation of CF3I to form CF3(-) and I, and we compare this process to the corresponding photolysis channel. By using the velocity slice imaging (VSI) technique we can visualize the complete dynamics of this process and show that electron-driven dissociation proceeds from the same initial parent state as the corresponding photolysis process. However, in contrast to photolysis, which leads nearly exclusively to the (2)P(1/2) excited state of iodine, electron-induced dissociation leads predominantly to the (2)P(3/2) ground state. We believe that the changed spin state of the negative ion allows an adiabatic dissociation through a conical intersection, whereas this path is efficiently repressed by a required spin flip in the photolysis process.

O(-) from amorphous and crystalline CO2 ices.

O(-) desorbed from amorphous and crystalline films of CO2 at 18 K under low energy electron impact is studied using time of flight mass spectrometry. The nature of the CO2 film is characterized by Fourier transform infrared spectrometry as a function of film thickness. It is found that the desorption rate from amorphous films is considerably larger than that from crystalline films. The desorption signal from the 4 eV resonance is found to be the dominant one as compared to that from the higher energy resonances, notably the one at 8 eV observed in the gas phase. This is explained in terms of the large enhancement in the dissociative electron attachment cross section for the 4 eV resonance in the condensed phase reported earlier using the charge trapping method.

Dissociative electron attachment to N2O using velocity slice imaging.

The structure and dynamics of the negative ion resonances leading to dissociative electron attachment in N2O are studied using the velocity slice imaging technique. Distinct momentum distributions are observed in the O(-) channel for the dominant resonances below 4 eV which are considerably different than those reported so far. Also the relatively weak but distinct resonances at 8.1 eV and 13.2 eV are studied for their dynamics for the first time. For each of these resonances two different channels of dissociation are observed with differing angular distributions.

Electron impact induced anion production in acetylene.

A detailed experimental investigation of electron induced anion production in acetylene, C2H2, in the energy range between 1 and 90 eV is presented. The anions are formed by two processes in this energy range: dissociative electron attachment (DEA) and dipolar dissociation (DD). DEA in C2H2 is found to lead to the formation of H(-) and C2(-)/C2H(-) through excitation of resonances in the electron energy range 1-15 eV. These anionic fragments are formed with super thermal kinetic energy and reveal no anisotropy in the angular distributions. DD in C2H2 leads to the formation of H(-), C(-)/CH(-) and C2(-)/C2H(-) with threshold energies of 15.7, 20.0 and 16.5 eV respectively. The measured anion yields have been used to calculate anion production rates for H(-), C(-)/CH(-) and C2(-)/C2H(-) in Titan's ionosphere.

Quantum superposition of target and product states in reactive electron scattering from CF4 revealed through velocity slice imaging.

Exploiting the technique of velocity slice imaging, we have performed a detailed study of reactive electron scattering with CF4. We have measured the electron impact energy dependence of both the angular and kinetic energy distributions of the channels yielding F- and CF3(-) anions. These data provide an unprecedented insight into the quantum superposition of the target state and product channels, respectively, of Td and C3v symmetry, and shed new light on the dissociation dynamics.

Dissociative electron attachment to acetaldehyde, CH3CHO. A laboratory study using the velocity map imaging technique.

A detailed experimental investigation of the dissociative electron attachment (DEA) process to acetaldehyde, CH(3)CHO is presented. To investigate this process we use a time of flight spectrometer coupled with the velocity slice imaging technique. DEA in CH(3)CHO is found to lead to the formation of CH(3)(-), O(-), OH(-), C(2)H(-), C(2)HO(-) and CH(3)CO(-) anionic products produced through scattering resonances in the electron energy range of 6 to 13 eV. Of these product ions only O(-) is formed with any measurable kinetic energy distribution indicating a two-body dissociation process. CH(3)CO(-), although formed with very low kinetic energy, shows anisotropy in the velocity slice image, indicating ejection of the H atom in the 180° direction with respect to the electron beam. The low kinetic energy distributions and absence of any anisotropy in the angular distributions of the other product ions indicate that they are formed through multiple fragmentation of the transient molecular negative ion. The angular distribution of O(-) is analysed in terms of the various partial waves.

Dissociative electron attachment resonances in ammonia: a velocity slice imaging based study.

Negative ion resonance states of ammonia are accessed upon capture of electrons with energy 5.5 eV and 10.5 eV, respectively. These resonance states dissociate to produce H(-) and NH(2)(-) fragment anions via different fragmentation channels. Using the velocity slice imaging technique, we measured the angular and kinetic energy distribution of the fragment H(-) and NH(2)(-) anions with full 0-2π angular coverage across the two resonances. The scattered H(-) ions at both resonances show variation in their angular distribution as a function of the kinetic energy indicating geometric rearrangement of NH(3)(-*) ion due to internal excitations and differ from the equilibrium geometry of the neutral molecule. The second resonance at 10.5 eV shows strong forward-backward asymmetry in the scattering of H(-) and NH(2)(-) fragment ions. Based on the angular distributions of the H(-) ions, the symmetry of the resonances at 5.5 eV and 10 .5 eV are determined to be A(1) and E, respectively, within C(3v) geometry.

Dissociative electron attachment cross sections for H2 and D2.

New measurements of the absolute cross sections for dissociative electron attachment (DEA) in molecular hydrogen and deuterium are presented which resolve previous ambiguities and provide a test bed for theory. The experimental methodology is based upon a momentum imaging time-of-flight spectrometer that allowed us to eliminate any contributions due to electronically excited metastable neutrals and ultraviolet light while ensuring detection of all the ions. The isotope effect in the DEA process in the two molecules is found to be considerably larger than previously observed. More importantly, it is found to manifest in the polar dissociation process (also known as ion pair production) as well.

Dissociative electron attachment to H2S probed by ion momentum imaging.

The dissociation dynamics of negative ion resonance states in H(2)S formed upon electron attachment are studied using momentum imaging of the fragment H(-) and S(-) ions and compared with similar resonances in water. The H(-) momentum images show that dissociation dynamics at the 5.2 eV resonance are very similar to those of the 6.5 eV (B(1)) resonance in water. Unlike the 8.5 eV resonance in water, which has A(1) symmetry but is found to display considerable deviation from the axial recoil approximation in the momentum distribution of H(-) ions, the distribution from the corresponding resonance in H(2)S at 7.5 eV is found to follow the axial recoil approximation fairly well. The resonance state with B(2) symmetry at 10 eV is found to decay via four dissociation channels viz.-H(-) + H + S, H(-) + SH(A(2)Σ), H(-) + SH(X(2)Π) and S(-) + H + H channels, similar to those that were seen in the B(2) resonance in water at 12 eV, including sequential fragmentation in the multiple fragmentation channels. However, the angular distributions for the fragment ions from this resonance are found to be distinctly different from those in water, even while displaying considerable deviation from the axial recoil approximation similar to that in water.

Dissociative electron attachment to NO probed by velocity map imaging.

An experimental and theoretical investigation of the dissociative electron attachment process in nitric oxide is presented. Measurements using the recently developed ion momentum imaging conclusively show the presence of two resonance features in the O(-) channel. These are found to dissociate to give N atoms in the (2)D and (2)P excited states respectively, thus settling the controversies regarding the possible dissociation limits of this process. Though the angular distribution of O(-) shows the resonances contributing to these dissociations are of Π symmetry and a mixture of Π and Σ or Δ symmetry respectively, our calculations using R-matrix theory show no direct electron attachment channel leading to O(-) through these resonances, as all the allowed resonances below 10 eV decay to either O + N(-) or O(-) + N((4)S) channels. We propose that indirect mechanisms through curve crossings lead to the experimentally observed results.