Low-energy electron-stimulated luminescence of thin H2O and D2O layers on Pt(111)

J Phys Chem B. 2005 Aug 25;109(33):15835-41. doi: 10.1021/jp044077b.


The electron-stimulated luminescence (ESL) from amorphous solid water and crystalline ice films deposited on Pt(111) at 100 K is investigated as a function of the film thickness, incident electron energy (5-1000 eV), isotopic composition, and film structure. The ESL emission spectrum has a characteristic double-peaked shape that has been attributed to a transition between a superexcited state (C) and the dissociative, first excited state (A) in water: C --> A. Comparing the electron-stimulated luminescence and O2 electron-stimulated desorption (ESD) yields versus incident electron energy, we find the ESL threshold is approximately 3 eV higher than the O2 ESD threshold, which is close to the center of the emission spectrum near 400 nm and supports the C --> A assignment for the ESL. For thin films, radiative and nonradiative interactions with the substrate tend to quench the luminescence. The luminescence yield increases with coverage since the interactions with the substrate become less important. The ESL yield from D2O is approximately 4-5 times higher than that from H2O. With use of layered films of H2O and D2O, this sizable isotopic effect on the ESL is exploited to spatially profile the luminescence emission within the ASW films. These experiments show that most of the luminescence is emitted from within the penetration depth of the incident electron. However, the results depend on the order of the isotopes in the film and can be modeled by assuming some migration of the electronically excited states within the film. The ESL is very sensitive to defects and structural changes in solid water, and the emission yield is significantly higher from amorphous films than from crystalline ice.