Metastable hydronium ions in UV-irradiated ice

We show that the irradiation of UV light (10-11 eV) onto an ice film produces metastable hydronium (H(3)O(+)) ions in the ice at low temperatures (53-140 K). Evidence of the presence of metastable hydronium ions was obtained by experiments involving adsorption of methylamine onto UV-irradiated ice films and hydrogen-deuterium (H∕D) isotopic exchange reaction. The methylamine adsorption experiments showed that photogenerated H(3)O(+) species transferred a proton to the methylamine arriving at the ice surface, thus producing the methyl ammonium ion, which was detected by low energy sputtering method. The H(3)O(+) species induced the H∕D exchange of water, which was monitored through the detection of water isotopomers on the surface by using the Cs(+) reactive ion scattering method. Thermal and temporal stabilities of H(3)O(+) and its proton migration activity were examined. The lifetime of the hydronium ions in the amorphized ice was greater than 1 h at ∼53 K and decreased to ∼5 min at 140 K. Interestingly, a small portion of hydronium ions survived for an extraordinarily long time in the ice, even at 140 K. The average migration distance of protons released from H(3)O(+) in the ice was estimated to be about two water molecules at ∼54 K and about six molecules at 100 K. These results indicate that UV-generated hydronium ions can be efficiently stabilized in low-temperature ice. Such metastable hydronium ions may play a significant role in the acid-base chemistry of ice particles in interstellar clouds.