Low-energy electron driven reactions in layered methanol/amorphous solid water films
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Understanding the radiolysis of impure water and resulting reactions is crucial to many fields. Reactions driven by low energy electrons (LEE) are of special interest, as high-energy radiation generates large quantities of these electrons, which then provide the energy for most subsequent reactions. Interfacially located reactions are also of particular interest, both as models for heterogeneously distributed reactions occurring during radiolysis, and in their own right, as radiation-driven reactions at interfaces are responsible for key processes such as corrosion and DNA damage. To study LEE-driven reactions at interfaces, thin-layered films of amorphous solid water (ASW) and methanol were grown under ultra-high vacuum conditions using molecular beam techniques. The films were exposed to a beam of low-energy (100eV or less) electrons, and studied using electron-stimulated desorption (ESD) and temperature programmed desorption (TPD). ESD studies indicated that methanol moves through a water film during deposition at 80 K but not at 50 K. This transport was not seen during thermal annealing, but radiation-induced mixing was observed at all temperatures. Major and minor LEE radiation products of pure methanol films were identified and found to be consistent with previous results. Products of LEE irradiated layered methanol/water films were determined for the first time using ESD and TPD spectra, and found to be limited to H₂, O, O₂, CH₂O, C₂H₆, CO, CO₂, CH₃OCH₃, and CH₃CH₂OH. The effect of adding methanol to an ASW film on the production in ASW of H₂ and O₂ was also examined. The interface created by the addition of CH₃OH to ASW was found to generate H₂ in previously non-reactive regions of the water film by increasing water-water and water-methanol reactions. Radiative mixing of CH₃OH and ASW enhanced this effect, presumably by increasing the region of disrupted H-bonding in the ASW. In contrast, the addition of CH₃OH at low coverages suppressed O₂ production in both unprocessed and preprocessed ASW layers. Modeling indicates that methanol scavenging of the O₂ precursor OH and of the reaction-driving electrons is responsible for this reduction in O₂ signal.