Site-dependent electron-stimulated reactions in water films on TiO2(110).

Electron-stimulated reactions in thin [<3 ML (monolayer)] water films adsorbed on TiO(2)(110) are investigated. Irradiation with 100 eV electrons results in electron-stimulated dissociation and electron-stimulated desorption (ESD) of adsorbed water molecules. The molecular water ESD yield increases linearly with water coverage theta for 0< or =theta< or =1 ML and 1<theta< or =2 ML. However, for theta>1 ML, the water ESD yield per additional water molecule adsorbed (i.e., the slope of the ESD yield versus coverage) is 3.5 times larger than for theta<1 ML. In contrast, the number of water molecules dissociated per incident electron increases linearly for theta< or =2 ML without changing slope at theta=1 ML. The total electron-stimulated sputtering rate, as measured by postirradiation temperature programmed desorption of the remaining water, is larger for theta>1 ML due to the increased water ESD for those coverages. The water ESD yields versus electron energy (for 5-50 eV) are qualitatively similar for 1, 2, and 40 ML water films. In each case, the observed ESD threshold is at approximately 10 eV and the yield increases monotonically with increasing electron energy. The results indicate that excitations in the adsorbed water layer are primarily responsible for the ESD in thin water films on TiO(2)(110). Experiments on "isotopically layered" films with D(2)O adsorbed on the Ti(4+) sites (D(2)O(Ti)) and H(2)O adsorbed on the bridging oxygen atoms (H(2)O(BBO)) demonstrate that increasing the water coverage above 1 ML rapidly suppresses the electron-stimulated desorption of D(2)O(Ti) and D atoms, despite the fact that the total water ESD and atomic hydrogen ESD yields increase with increasing coverage. The coverage dependence of the electron-stimulated reactions is probably related to the different bonding geometries for H(2)O(Ti) and H(2)O(BBO) and its influence on the desorption probability of the reaction products.