Photodissociation of water clusters doped with HX(X=Br,Cl), molecules has been studied in a molecular beam experiment. The HX(H2O)n clusters are dissociated with 193 nm laser pulses, and the H fragments are ionized at 243.07 nm and their time-of-flight distributions are measured. Experiments with deuterated species DBr(H2O)n and HBr(D2O)n suggest that the photodissociation signal originates from the presence of the HX molecule on the water cluster, but does not come directly from a photolysis of the HX molecule. The H fragment is proposed to originate from the hydronium molecule H3O. Possible mechanisms of the H3O production are discussed. Experimental evidence suggests that acidic dissociation takes place in the cluster, but the H3O+ ion remains rather immobile.

J Heyrovský Institute of Physical Chemistry Academy of Sciences of the Czech Republic Prague 8 Czech Republic

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