highlight 10 2019

Radical ions are important intermediates in a variety of chemical and biochemical reactions, but the dynamics of their excited states in liquid solution is still poorly understood. Interest in these dynamics has undergone a “renaissance” in recent years as, in addition to fundamental interest, various groups internationally have rediscovered the possibility of using these excited states to do highly exergonic electron transfer chemistry with relatively low-energy photons.

We have recently measured the excited state dynamics of two anthracene derivative anions, A and B using transient electronic absorption spectroscopy. These are presented above (a and b for compound A, c and d for compound B). Both derivatives show qualitatively similar behaviour – an initial c. 7 ps decay from the excited state and then cooling on the ground state surface. Analysing the cooling on the ground state surface alone by using spectral reconstruction techniques, we found that compound B cools more slowly than compound A. This was explained using DFT calculations, which showed that compound A had more low-energy modes able to couple to the surrounding solvent.

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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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