The dynamics of photofragments produced in ordered molecular layers adsorbed on surfaces are intimately connected to the electronic properties of the surface and the physical structure of the layer. These dynamics have been most often studied by examining the gaseous fragments expelled into the vacuum by using angularly-resolved time-of-flight mass spectrometry (TOF-MS), with or without internal (vibrational and rotational) state selectivity. The angular distribution of these fragments can be correlated with collisional encounters that occur in specific oriented and aligned geometries. Controlling the adlayer structure, and hence the photodynamics, is therefore a possible method for control of surface chemical reaction. Examples from recent studies of methyl halides adsorbed on LiF(001), NaCl(001), MgO(001) and TiO2(110) will be presented to illustrate how angle- resolved TOF-MS data can be used to provide insight into both the structure and photodynamics of adsorbed molecules. In at least one of these cases, the unique collision dynamics of the adsorbed state produced reaction products that were not observed in gas phase molecule photochemistry.
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