Perylene-rare-gas heteroclusters. I. Electronic spectroscopy

Dar Bahatt*, Andreas Heidenreich, Narda Ben-Horin, Uzi Even, Joshua Jortner

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

22 Scopus citations


In this paper we report on the electronic two-photon two-color near threshold spectroscopy of mass-resolved perylene-Arn (n=1-45), perylene-Krn (n=1-35), perylene·(N2)n (n=1-12), and perylene·(CH4)n (n=1-10) heteroclusters. The S0→S1 inhomogeneously broadened spectra of perylene·Arn (n=1-6) and perylene·Kr n (n=1-4) exhibit resolved spectral features, which were assigned on the basis of experimental combination rules and polarizability relations to the electronic origins of distinct two-sided and one-sided structural isomers. Larger perylene·An (A=Ar, Kr; n=6-10) heteroclusters exhibit an "abnormal" specific size dependence of the red spectral shifts, which decrease with increasing n and reach a local minimum at n=8. Similar characteristics of the red spectral shifts are exhibited for perylene"(N2)n and perylene·(CH 4)n (n=4-8) heteroclusters. This abnormal size dependence of the spectral shifts is attributed to the dominance of one-sided single-layered and double-layered structural isomers in this cluster size domain. On the basis of the comparison between the spectroscopic data and molecular dynamics simulations of the absorption line shapes we have obtained a quantitative description of isomer-specific structures for n=2-6, a semiquantitative description of the abnormal size domain for n=6-10 (due to the dominance of one-sided structures with the abundance of two-layered structures increasing at higher n), the prevalence of one-sided structures for n=16 and n=22, and the realization of two-sided multilayered structures at n=45.

Original languageEnglish
Pages (from-to)6290-6299
Number of pages10
JournalThe Journal of Chemical Physics
Issue number9
StatePublished - 1994


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