Abstract
Thermal and photo-decomposition of Fe(CO)5 adsorbed on silver surfaces have been studied using reflection absorption IR spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS), temperature programmed desorption (TPD) technique, and synchrotron orbital radiation (SOR). Fe(CO)5 is found to chemisorb at <120 K partly on the silver surfaces cleaned by Ar ion sputtering. Chemisorbed Fe(CO)5 undergoes thermal decarbonylation at >180 K to form Fe(CO)4 which decomposes completely at >300 K. Photolysis of adsorbed Fe(CO)5 leads to formation of subcarbonyl species which CO/Fe ratio is ca. 4, irrespective of the type of adsorption, when its coverage is not greater than monolayer. With increase in the coverage, further photo-decarbonylation occurs to produce oligomer species which CO/Fe ratio is less than 4. Yield of photo-decarbonylation increases with increasing coverage up to 20 monolayers, indicating considerable energy relaxation of photo-excited species near the surface. Geometry of intermediate species is discussed in terms of a surface selection rule of IRAS. intermediate species.
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