Ultrafast photoinduced dynamics of halogenated cyclopentadienes: Observation of geminate charge-transfer complexes in solution


The photoinduced dynamics of the fully halogenated cyclopentadienes C5Cl6 and C5Br6 have been investigated in solution and gas phase by femtosecond time-resolved spectroscopy. Both in solution and in gas phase, homolytic dissociation into a halogen radical and a C5X5 radical were observed. In liquid phase, solvent-dependent formation of charge transfer complexes between geminate radicals was observed for the first time. These complexes were found to be surprisingly stable and offered the opportunity to follow the dynamics of specific radical pairs. In the case of C5Cl6 in trichloroethanol, a reaction of the chlorine radical with molecules from the solvent cage was observed.

Physical Chemistry Chemical Physics
Thomas Wolf
Thomas Wolf
Staff Scientist

My research is focused on discovering structure-function relationships in ultrafast photochemistry to better understand and eventually control this type of reactions.