RESUMO
The interaction of HCl with the D(2)O-ice surface has been investigated in the temperature range 15-200 K by utilizing time-of-flight secondary ion mass spectroscopy, temperature-programmed desorption, and x-ray photoelectron spectroscopy. The intensities of sputtered H(+)(D(2)O) and Cl(-) ions (the H(+) ions) are increased (decreased) markedly above 40 K due to the hydrogen bond formation between the HCl and D(2)O molecules. The HCl molecules which form ionic hydrates undergo H/D exchange at 110-140 K and a considerable fraction of them dissolves into the bulk above 140 K. The neutral hydrates of HCl should coexist as evidenced by the desorption of HCl above 170 K. They are incorporated completely in the D(2)O layer up to 140 K. The HCl molecules embedded in the thick D(2)O layer dissolve into the bulk, and the ionic hydrate tends to segregate to the surface above 150 K.
RESUMO
TOF-SIMS is used to investigate the interactions between D2O and hydrophobic molecules, such as CH4, CH3F, CH2F2, CHF3, and CF4, at cryogenic temperatures (15 K). By irradiation with a 1.5-keV He+ beam, the D(+)(D2O)n ions are ejected efficiently from the D2O nanoclusters physisorbed on the CF4 layer due to Coulomb explosion: the ion yields are by about two orders of magnitude higher than those from a thick D2O layer via the kinetic sputtering. The D(+)(D2O)n yields decrease on the CHnF(4-n) layer with increasing the number of the C-H group. This is because the Coulombic fission is quenched due to the delocalization of valence holes through the C-H...H-C and C-H...D2O contacts. A pure D2O film is hardly grown on the CH4 layer as a consequence of intermixing whereas the D2O molecules basically adsorb on the surfaces of fluoromethanes, suggesting the attractive (water-repellent) interactions in the C-H...D2O (C-F...D2O) contacts. The C-H...O bond behaves like a conventional O-H...O hydrogen bond as far as the collision-induced proton transfer reaction is concerned.
