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Two examples of structural investigation of photogenerated short-lived transient species of aromatic compounds, by using time-resolved electronic absorption and resonance Raman spectroscopy are provided. The picosecond Raman spectra of the lowest excited singlet state (S 1 ) of 4,4′-bipyridine and 2,2′-bipyridine in solution are discussed first. The results provide strong evidence for a surprising asymmetric S 1 structure in which the electronic excitation and the consequent structural distortion are localized in one of the pyridyl rings, the other ring being almost unaffected. The laser photolysis of biphenyl occluded in the pores and cavities of ZSM-5 and faujasitic zeolites have been investigated in the nanosecond time-scale as functions of aluminium content, the extraframework cations, sample loading and intensity of photolysis. At low pump power and low aluminium content the triplet state of biphenyl is observed. At higher pump power and in aluminated zeolites, biphotonic ionization was observed to generate the cation radical. As the loading increased, the anion radical yield increased. This is characteristic of faujasitic zeolites in which scavenger molecules with restricted diffusional motions are confined in the vicinity of photoionized molecules. The lifetimes of cation radical were particularly long in aluminated ZSM-5 zeolites with efficient trapping sites of the photoejected electron. |
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