Interaction of carboxylic acids and water ice probed by argon ion induced chemical sputtering

Abstract

In this paper, we investigated the interaction of simple carboxylic acids, formic acid (FA), acetic acid (AA), and propionic acid (PA) with thin layers of water ice in the temperature range of 110-190 K in ultrahigh vacuum. The focus, however, is on the AA-ice system. Molecularly thin layers of these systems were prepared on a pre-cooled polycrystalline copper substrate. The interactions and phase changes in the system were monitored with chemical sputtering using low-energy (≤30 eV) Ar⁺, which probes the topmost surface layers. At 110 K, the deposited AA exists as dimers in its amorphous solid form. At the same temperature, in the presence of water ice, this dimeric form gets converted to chainlike oligomers. Chemical sputtering spectra show distinct features for these two surface species. The data suggest that ion formation reflects the surface structure, implying a unique mechanism for its formation. Detailed studies have been made with amorphous solid water (ASW) and crystalline water (CW) to get a complete understanding of the system. Experiments carried out with AA-D₂O ice confirmed the proton-transfer mechanism during chemical sputtering. Other studies were conducted with AA-CH₃OH and AA-CCl₄ systems. Detailed investigations performed to understand the effect of thickness of AA and ice overlayers suggest that the extent of water molecules required to effect the structural transformation in the acid is dependent on the amount of the latter. Dimeric-to-oligomeric transformation does not occur for the PA-ice system. Detection of a structural transition at the very top of ice in molecularly thin films adds additional capabilities to the low-energy ion scattering technique.