Charge-transfer photodissociation of adsorbed molecules via electron image states

Abstract

The 248nm and 193nm photodissociation of submonolayer quantities of CH${}_3$Br and CH${}_3$I adsorbed on thin layers of n-hexane indicate that the dissociation is caused by dissociative electron attachment from sub-vacuum level photoelectrons created in the copper substrate. The characteristics of this photodissociation-- translation energy distributions and coverage dependences show that the dissociation is mediated by an image potential state which temporarily traps the photoelectrons near the n-hexane--vacuum interface, and then the charge transfers from this image state to the affinity level of a co-adsorbed halomethane which then dissociates.

submitted to Journal of Chemical Physics