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The near ultraviolet photodissociation dynamics of silver atom rare gasdimers have been studied by velocity map imaging. AgRG (RG = Ar, Kr, Xe)species generated by laser ablation are excited in the region of the C <- Xcontinuum leading to direct, near threshold dissociation generating Ag* (2P3/2)+ RG (1S0) products. Images recorded at excitation wavelengths throughout the C<- X continuum, coupled with known atomic energy levels, permit determinationof the ground X (2SIGMA+) state dissociation energies of 85.9 +/- 23.4 cm-1(AgAr), 149.3 +/- 22.4 cm-1 (AgKr) and 256.3 +/- 16.0 cm-1 (AgXe). Threeadditional photolysis processes, each yielding Ag atom photoproducts, areobserved in the same spectral region. Two of these are markedly enhanced inintensity upon seeding the molecular beam with nitrous oxide, and are assignedto photodissociation of AgO at the two photon level. These features yield animproved ground state dissociation energy for AgO of 15965 +/- 81 cm-1, whichis in good agreement with high level calculations. The third process results inAg atom fragments whose kinetic energy shows anomalously weak photon energydependence and is assigned tentatively to dissociative ionization of the silverdimer Ag2.

Dissociation energies of AgRG (RG = Ar, Kr, Xe) and AgO molecules from velocity map imaging studies