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Probing the Interaction of Hydrogen Chloride with Low-Temperature Water Ice Surfaces Using Thermal and Electron-Stimulated Desorption

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School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332, United States
*E-mail: [email protected]. Phone: (404) 894-4012. Fax: (404) 894-7452.
Cite this: J. Phys. Chem. A 2011, 115, 23, 5936–5942
Publication Date (Web):May 6, 2011
Copyright © 2011 American Chemical Society

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    The interaction and autoionization of HCl on low-temperature (80–140 K) water ice surfaces has been studied using low-energy (5–250 eV) electron-stimulated desorption (ESD) and temperature programmed desorption (TPD). There is a reduction of H+ and H2+ and a concomitant increase in H+(H2O)n=1–7 ESD yields due to the presence of submonolayer quantities of HCl. These changes are consistent with HCl induced reduction of dangling bonds required for H+ and H2+ ESD and increased hole localization necessary for H+(H2O)n=1–7 ESD. For low coverages, this can involve nonactivated autoionization of HCl, even at temperatures as low as 80 K; well below those typical of polar stratospheric cloud particles. The uptake and autoionization of HCl is supported by TPD studies which show that for HCl doses ≤0.5 ± 0.2 ML (ML = monolayer) at 110 K, desorption of HCl begins at 115 K and peaks at 180 K. The former is associated with adsorption of a small amount of molecular HCl and is strongly dependent on the annealing history of the ice. The latter peak at 180 K is commensurate with desorption of HCl via recombinative desorption of solvated separated ion pairs. The activation energy for second-order desorption of HCl initially in the ionized state is 43 ± 2 kJ/mol. This is close to the zero-order activation energy for ice desorption.

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