In this contribution photochemical processes in pure rare gas clusters will be discussed. The relaxation dynamics of electronically excited He clusters is investigated with luminescence spectroscopy. After electronic excitation of He clusters many sharp lines are observed in the visible and infrared spectral range which can be attributed to He atoms and molecules desorbing from the cluster. It turns out that the desorption of electronically excited He atoms and molecules is an important decay channel. The findings for He ch.nsters are compared with results for Ar clusters. While desorption of electronically excited He atoms is observed for all clusters containing up to several thousand atoms a corresponding process in Ar clusters is only observed for very small clusters (N < 10).
PACS36.40.−C Atomic and molecular clusters 82.50.−m Photochemistry and radiation chemistry 78.55:−m Photoluminescence
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