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Exciplex and excimer formation have been probed in several jet cooled complexes using mass selective two-photon ionisation and fluorescence excitation spectroscopy as well as ground state depletion spectroscopy (hole burning): (i) In the anthracene-dimethyl-ortho-toluidine system, it has been found that the ionisation step takes place with a much higher efficiency from the charge transfer state responsible for the exciplex emission than from the locally excited state giving rise to the resonant fluorescence. (ii) The dimer, trimer, and higher clusters of anthracene all show only excimer emission. When compared to the dimer, the trimer exhibits a peculiar behaviour (structured fluorescence excitation and hole burning spectra, short lifetime and low ionisation efficiency) which has been related to a significant locally excited character of the initially prepared state of the species excited state. (iii) The influence of an intermolecular hydrogen bond on the electron transfer process has been studied in the 2,2,2-trifluoro-1-(9-anthryl)ethanol- dimethylaniline system. A threshold for exciplex formation higher than in the case of the anthracene-dimethylaniline complex is observed.
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