Photochemistry of adsorbed molecules. III. Photodissociation and photodesorption of CH3Br adsorbed on LiF(001)

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Abstract
Submonolayers of CH3Br physisorbed on a LiF(001) surface were irradiated by pulsed ultraviolet (UV) in ultrahigh vacuum in a study of surface aligned photochemistry (SAP). Translational energy and angular distributions were obtained for both photofragments and photodesorbed molecules by angularly resolved time of flight to a mass spectrometer. Single‐photon adsorbate photolysis (PDIS) led to photofragment distributions, CH3 and Br, which differed from gas‐phase photolysis. Photodesorption (PDES) of CH3Br was nonthermal and arose from UV absorption by the LiF crystal. The dynamics for these photoprocesses were found to vary in an informative way with the coverage and the phase of the adsorbed layer.

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