Photophysics and photochemistry of I 2 (D, D′) in rare gas clusters

• Published in: Chemical physics Vol. 211; no. 1; pp. 377 - 386
• Main Authors: Randall, Karen L., Donaldson, D.J.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01-11-1996
• ISSN: 0301-0104
• DOI: 10.1016/0301-0104(96)00207-8

We report the resolved fluorescence spectra of I
2, clustered with Ar, Kr and Xe and excited at 193 nm to the D state of the first ion-pair manifold. In Ar and Kr clusters, a broad, featureless emission band is seen, which shifts to lower energies as the cluster size increases. In Xe clusters, this band is not observed; there is very efficient quenching of all emission. Under some expansion conditions, XeI
∗ excimer emission is observed with a two-photon dependence on the intensity of the 193 nm excitation laser. These results are all explained by a model in which excitation of I
2 into the ion-pair manifold is followed by a harpooning-type electron transfer and formation of an excited charge transfer complex between I
2 and a rare gas atom.