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

Dynamics of Dissociative Electron Attachment to Aliphatic Thiols

Dissociative electron attachment (DEA) shows functional group-dependent site selectivity in the $H^-$ ion channel. In this context, the thiol functional group has yet to be studied in great detail, although this functional group carries importance in radiation damage studies where the low-energy secondary electrons are known to induce damage through the DEA process. We report detailed measurements of absolute cross-sections and momentum images of various anion fragments formed in the DEA process in simple aliphatic thiols. We also compare the observed dynamics with that reported earlier in hydrogen sulphide, the precursor molecule for this functional group and also with aliphatic alcohols. Our findings show substantial resemblance in the underlying dynamics in these compounds and point to a possible generalisation of these features in the DEA to thiols. We also identify various pathways that contribute to the $S^-$ and $SH^-$ channels

Dynamics of the dissociative electron attachment to Ethanol

We report the detailed dynamics of the site selectivity observed in the dissociative electron attachment (DEA) process in ethanol based on the momentum images obtained using the velocity slice imaging technique. The H- dissociation channel shows the site selectivity where the anion signal from the O-H site peaks at 6.5 eV and 8 eV, and that from the C-H site peaks at 9.5 eV. The momentum images also show the two-body dissociation dynamics for the O-H site break-up. This dissociation channel shows a substantial effect of the torsion mode of vibrations on the electron attachment process. In contrast, the C-H site dissociation results from the many-body break-up consistent with the earlier reports of DEA dynamics from organic molecules. We have also found that the OH- channel has a resonance at 9.3eV and is produced with very little kinetic energy. Using the isotope substitution, we show the role of H atom scrambling in the C-O bond dissociation leading to the OH- channel. This channel shows a substantial deviation from the corresponding photodissociation dynamics

Electron attachment and quantum coherence in molecular hydrogen

Single electron attachment to a molecule may invoke quantum coherence in different angular momentum transfer channels. This has been observed in the 14 eV dissociative electron attachment resonance in molecular hydrogen where a coherent superposition of two negative ion resonant states of opposite parity is created, with the s and p partial waves of the electron contributing to the attachment process. Interference between the two partial wave contributions leads to a forward – backward asymmetry in the angular distribution of the product negative ions. Since these two resonant states dissociate to the same n = 2 state of H and H−, this asymmetry is further modified due to interference between the two paths of the dissociating molecular negative ion along different potential energy curves. This interference manifests as a function of the electron energy as well as isotopic composition. This case is akin to the quantum interference observed in photodissociation by one-photon vs two-photon absorption

Velocity slice imaging for dissociative electron attachment

A velocity slice imaging method is developed for measuring the angular distribution of fragment negative ions arising from dissociative electron attachment (DEA) to molecules. A low energy pulsed electron gun, a pulsed field ion extraction, and a two-dimensional position sensitive detector consisting of microchannel plates and a wedge-and-strip anode are used for this purpose. Detection and storage of each ion separately for its position and flight time allows analysis of the data offline for any given time slice, without resorting to pulsing the detector bias. The performance of the system is evaluated by measuring the angular distribution of O− from O2 and comparing it with existing data obtained using conventional technique. The capability of this technique in obtaining forward and backward angular distribution data is shown to have helped in resolving one of the existing problems in the electron scattering on O2

Effect of Background Signal on Momentum Imaging

The velocity Slice Imaging technique has revolutionised electron molecule interaction studies. Multiple electrostatic lens assemblies are often used in spectrometers for resolving low kinetic energy fragments. However, in a crossed-beam experiment with an effusive molecular beam, the extended source of ion generation due to the presence of the background gas creates artefacts on the momentum images as we try to magnify them beyond a certain size. Here, we present a systematic study of this effect on momentum imaging and the solutions to address this issue by background subtraction with suitable magnification. Additionally, we demonstrated that a supersonic molecular beam target helps minimise these artefacts in the image magnification by reducing the background signal. These systematic findings may bring valuable insight into the investigation of low kinetic energy release processes involving electron impact, ion impact, and merge beam experiments with large interaction volumes where high magnification is needed

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