Abstract
We studied the H/D exchange kinetics of pure and acid dopped water-ice film by using the techniques of reactive ions scattering (RIS) and low energy sputtering (LES) with low kinetic energy cesium ion beam (<35 eV). From RIS, neutral water isotopomers were detected in the form of cesium-molecule ion clusters, $CsX^+$ (X= $H_2O$, HDO, $D_2O$). Ionic species, like $H_3O^+$, $DH_2O^+$, $D_2HO^+$, $D_3O^+$, adsorbed on the surface were ejected via LES process. Those techniques allowed us to trace the isotopomeric populations of water-ice film. To show the catalytic effect of excess proton in the H/D exchange reaction, our study was conducted with two types of water-ice films. In film 1, about 0.5 BL of $H_2O$ was adsorbed on HCl (0.1 ML) dopped $D_2O$ (8 BL) film. In film 2, similar amount of $H_2O$ used in film 1 was adsorbed on pure $D_2O$ film. Kinetic data were obtained from each film type for 90-110 K (film 1) and 110-130 K (film 2) and fitted with numerically integrated lines. Through the Arrhenius plot of kinetic coefficient deduced from fitting of the H/D exchange reaction, the activation energy of film 1 and 2 were estimated to be $10{\pm}3kJmol^{-1}$ and $17{\pm}4kJmol^{-1}$. This activation barrier difference could be understood from detailed pictures of H/D exchange. In film 2, both the formation of ion pair, $H_3O^+$ and OH. and proton transfer were needed for the H/D exchange. However, in film 1, only proton transfer was necessary but ion pair formation was not, so this might reduce the activation energy.