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Supersonic-jet luminescence spectroscopy was applied to study vibronictransitions in icosahedral N2 and Ar-N2 clusters having from 100 to 400particles per cluster. In the case of mixed Ar-N2 clusters, the w->Xtransitions were observed to occur in single N2 molecules in an Ar environment,that is very much in the same way as in Ar-N2 bulk samples. In N2 clusters,however, a band series was detected which was never observed earlier. In thespectra of Ar-N2 clusters, this new series coexisted with the 'bulk' w->Xtransitions. Our analysis demonstrated that the series should be assigned toemission of van der Waals (N2)2 dimers from inside clusters. Earlier, suchdimers were only observed in molecular beams and gaseous nitrogen, this paperreports their observation in the solid phase of nitrogen suggesting that theymay be the basic building blocks of small N2 clusters. Our results can be ofinterest from the viewpoint of producing polymeric nitrogen since (N2)2 dimerscan be considered to be a starting species for its synthesis.

Observation of (N2)2 dimers in free nitrogen and argon-nitrogen clusters