Matrix interactions with rare-gas oxide excimers

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Abstract
Matrix interactions of rare-gas oxide molecules formed in solid matrices were studied by photoluminescence. Excitation energies between 8–12 eV were provided by both synchrotron radiation at the Stanford Synchrotron Radiation Laboratroy (SSRL) and a hydrogen discharge source at UCSB. Photoluminescence emission and excitation spectra of Ar:CO2(1%), Kr:CO2(1%), Kr:N2O(1%), and Kr:O2(1%) mixtures were obtained. Radiative lifetimes of ArO and KrO emissions from CO2 doped Ar and Kr matrices were also measured. The direct photodissociative threshold of CO2 to CO(X 1S+)+O(1S) in an Ar matrix was found to be 10.6 eV, in agreement with that of the gas phase. Further unambiguous evidence for radiationless, dissociative energy transfer, between the matrix free exciton and CO2, probably by a harpooning mechanism, was seen in Kr:CO2 below the direct photodissociation threshold. Temperature, matrix annealing, and character of the photofragment were found to have significant effects on the rare-gas oxide molecular binding and production rate.