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The mechanisms for photodissociation of methyl halides (CH$_3$X, X= Cl, Br,I) have been studied for these molecules when adsorbed on thin films ofC$_6$H$_6$ or C$_6$F$_6$ on copper single crystals, using time-of-flightspectroscopy with 248nm and 193nm light. For CH$_3$Cl and CH$_3$Br monolayersadsorbed on C$_6$H$_6$, two photodissociation pathways can be identified:neutral photodissociation similar to the gas-phase, and a dissociative electronattachment (DEA) pathway due to photoelectrons from the metal. The same methylhalides adsorbed on a C$_6$F$_6$ thin film display only neutralphotodissociation, with the DEA pathway entirely absent due to intermolecularquenching via a LUMO-derived electronic band in the C$_6$F$_6$ thin film. ForCH$_3$I adsorbed on a C$_6$F$_6$ thin film, illumination with 248nm lightresults in CH$_3$ photofragments departing due to neutral photodissociation viathe A-band absorption. When CH$_3$I monolayers on C$_6$H$_6$ thin films areilluminated at the same wavelength, additional new photodissociation pathwaysare observed that are due to absorption in the molecular film with energytransfer leading to dissociation of the CH$_3$I molecules adsorbed on top. Theproposed mechanism for this photodissociation is via a charge-transfer complexfor the C$_6$H$_6$ layer and adsorbed CH$_3$I.

Contrasting Mechanisms for Photodissociation of Methyl Halides Adsorbed on Thin Films of C$_6$H$_6$ and C$_6$F$_6$