The role of direct and substrate excitation in ultraviolet photolysis of phosgene on Pt(111)

The photodissociation rate of phosgene (Cl2CO) adsorbed on Pt(111) has been measured as a function of photon energy at normal incidence and as a function of incident angle using p-polarized light. Compared to the gas phase, the wavelength dependence of the initial photolysis cross section on the surface is redshifted. The angular response to p-polarized light is wavelength dependent. Above 315 nm, the angular dependence correlates with calculated metal absorption. At 280 nm, the angular dependence is much too strong to be accounted for solely by substrate excitation. A combination of substrate and direct excitation is adequate. This is the first direct evidence, for monolayers on metals, that both direct and substrate excitation contribute to surface photochemistry but dominate at different wavelengths.