[en] We have established through simulations and experiments the area over which Velocity Map Imaging (VMI) conditions prevail. We designed a VMI setup in which we can vary the ionization position perpendicular to the center axis of the time-of-flight spectrometer. We show that weak extraction conditions are far superior over standard three-plate setups if the aim is to increase the ionization volume without distorting VMI conditions. This is important for a number of crossed molecular beam experiments that already utilize weak extraction conditions, but to a greater extent for surface studies where fragments are desorbed or scattered off a surface in all directions. Our results on the dissociation of NO₂ at 226 nm show that ionization of the fragments can occur up to ±5.5 mm away from the center axis of the time-of-flight spectrometer without affecting resolution or arrival position.

[en] Low-energy (100 eV) electron-stimulated reactions in layered H₂O/CO/H₂O ices are investigated. For CO layers buried in amorphous solid water (ASW) films at depths of 50 monolayers (ML) or less from the vacuum interface, both oxidation and reduction reactions are observed. However, for CO buried more deeply in ASW films, only the reduction of CO to methanol is observed. Experiments with layered films of H₂O and D₂O show that the hydrogen atoms participating in the reduction of the buried CO originate in the region that is 10–50 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried CO layers, the CO reduction reactions quickly increase with temperature above ∼60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol to account for the observations

[en] The authors describe the application of a combination of velocity map imaging and time-of-flight (TOF) techniques to obtain three-dimensional velocity distributions for surface photodesorption. They have established a systematic alignment procedure to achieve correct and reproducible experimental conditions. It includes four steps: (1) optimization of the velocity map imaging ion optics' voltages to achieve optimum velocity map imaging conditions; (2) alignment of the surface normal with the symmetry axis (ion flight axis) of the ion optics; (3) determination of TOF distance between the surface and the ionizing laser beam; (4) alignment of the position of the ionizing laser beam with respect to the ion optics. They applied this set of alignment procedures and then measured Br(²P_3/2) (Br) and Br(²P_1/2) (Br*) atoms photodesorbing from a single crystal of KBr after exposure to 193 nm light. They analyzed the velocity flux and energy flux distributions for motion normal to the surface. The Br* normal energy distribution shows two clearly resolved peaks at approximately 0.017 and 0.39 eV, respectively. The former is slightly faster than expected for thermal desorption at the surface temperature and the latter is hyperthermal. The Br normal energy distribution shows a single broad peak that is likely composed of two hyperthermal components. The capability that surface three-dimensional velocity map imaging provides for measuring state-specific velocity distributions in all three dimensions separately and simultaneously for the products of surface photodesorption or surface reactions holds great promise to contribute to our understanding of these processes.

[en] Recent progress that has been made towards understanding the dynamics of collisions at the gas-liquid interface is summarized briefly. We describe in this context a promising new approach to the experimental study of gas-liquid interfacial reactions that we have introduced. This is based on laser-photolytic production of reactive gas-phase atoms above the liquid surface and laser-spectroscopic probing of the resulting nascent products. This technique is illustrated for reaction of O(³P) atoms at the surface of the long-chain liquid hydrocarbon squalane (2,6,10,15,19,23-hexamethyltetracosane). Laser-induced fluorescence detection of the nascent OH has revealed mechanistically diagnostic correlations between its internal and translational energy distributions. Vibrationally excited OH molecules are able to escape the surface. At least two contributions to the product rotational distributions are identified, confirming and extending previous hypotheses of the participation of both direct and trapping-desorption mechanisms. We speculate briefly on future experimental and theoretical developments that might be necessary to address the many currently unanswered mechanistic questions for this, and other, classes of gas-liquid interfacial reaction