Photochemistry at Structured Surfaces: A Classical Electromagnetic Approach

摘要

This review article discusses several important aspects of photochemistry at structured metallic surfaces. The electromagnetic field above the surface is calculated using the Rayleigh expansion. Conditions under which this expansion is valid and simplifying approximations which make it easier to use are discussed in detail. This formalism is then applied to three different but related phenomena. First, the photodissociation rate of a molecule above a surface is calculated for laser frequencies at or near the surface plasmon resonance. It is found that there is an optimal molecule-surface distance for photodissociation. Then the absorption lineshape of a molecule is considered, where both Fano and Lorentzian lineshapes are found to be distorted as the molecule approaches the surface. Finally, laser-induced periodic deposition is discussed, and a model is developed to describe the growth rate of a cadmium grating.