Theoretical Studies of Surface Reactions on Metals and Electronic Materials.

摘要

A synopsis of these studies follows, and, in a separate section, abstracts of published and submitted papers are provided. One of the goals of this research is to learn more about fundamental processes involving photoinduced electron transfer to adsorbates on metals, in particular, those that lead to dissociation of water. Silver nanoparticles are chosen to represent the low end of catalytic activity, so as to delineate effects most directly associated with the dissociative electron transfer step. However, we also worked on palladium nanoparticles to take advantage of increased reactivity of that metal and its potential for hydrogen storage. In collaborative work with experimental investigations, the palladium catalyzed decomposition of butanoic acid was treated using high level electronic structure theory. For photoinduced processes at surfaces, key questions involve how electron transfer excited states are stabilized by the image charge or hole in the metal and whether dissociation occurs on the excited electronic state surface or by crossing over at some adsorbate geometry to the ground state surface. Differentiating between competing pathways depends on energy barriers and lifetimes in excited states.