DOI: 10.1021/acs.jpcc.6c03846 ISSN: 1932-7447

Reaction of a Laser-Ablated Al Plume with a Fluorinated Ionic-Liquid Surface: Characterizing the AlF-Producing Species

Philip A. J. Pearcy, Paul. D. Lane, Peter T. Rubli, Christian T. Haakansson, Peter D. Watson, Stuart R. Mackenzie, Naomi S. Elstone, Duncan. W. Bruce, John M. Slattery, Matthew L. Costen, Kenneth G. McKendrick

Abstract

The species present in a laser-ablated Al plume have been characterized and their reactivity with the surface of the ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][Tf2N]), has been investigated. Al atoms were confirmed to be present and their kinetic-energy distributions determined by laser-induced fluorescence time-of-flight measurements, over a wider range of ablation fluences than reported previously. Cations were detected directly using an in-line microchannel-plate-detector assembly. Corroboratory measurements of the ions entrained in a He buffer gas confirmed Al+ to be the only cation present in measurable concentrations. The Al+ kinetic energies were determined by time-of-flight and found to be much hotter than anticipated based on previous independent reports; under the highest-fluence conditions examined (30 mJ pulse–1, nominal fluence of 42 J cm–2), the mean kinetic energies of Al and Al+ were 17 and 450 eV, respectively. Using an electrostatic deflector, it was shown that both Al and Al+ projectiles produce AlF through reaction at the surface of the ionic liquid [C2mim][Tf2N] containing a fluorinated anion. The AlF yield from Al+ is mildly dominant under our conditions. AlF leaves the surface with near-thermal kinetic energy and rotational distributions. There is a minor component of vibrationally excited AlF which is confined to the fastest products. The observation of near-complete thermalization of the AlF products is consistent with significant penetration of the projectiles into the liquid, as would be anticipated from the high incident kinetic energies, particularly for Al+. The results provide new insights into reactive-atom scattering (RAS) from fluorine-containing liquid surfaces.

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