highlight 6 2018

We want to understand the nature of the product in bimolecular photoinduced charge separation (CS) – i.e. ion pairs. We are exploring whether the excited-state dynamics of the constituting radical ions report on the change of the distribution of the CS product from largely tight/contact ion pairs to free ions.  

We accomplish this using pump-pump-probe (PPP) spectroscopy. A first pump pulse triggers photoinduced CS and, after a defined time delay, a transient electronic absorption measurement is carried out on the ensuing ion population. An example of such data shown above reveals that - as one changes from long to short waiting times, an additional spectral component arises in the red (Figure a) and the bleach decay kinetics change (Figure b). This implies that the excited-state dynamics of radical ions depend on whether the ion is paired or free and, thus, that one can use these dynamics as a kind of “molecular ruler”.

 

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Eric Vauthey

Physical Chemistry Department - Sciences II - University of Geneva
30, Quai Ernest Ansermet - CH-1211 Geneva 4 (Switzerland)


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