Sub-50 fs Formation of Charge Transfer States Rules the Fate of Photoexcitations in Eumelanin-Like Materials.

Eumelanins play a crucial role as photoprotective agents for living organisms, yet the nature of the stationary and transient species involved in the light absorption and deactivation processes remains controversial. Moreover, the critical sub-100 fs time scale, which is key to the characterization of the primary excited species, has remained unexplored. Here, we study the eumelanin analogue polydopamine (PDA) and employ a combination of steady-state and transient optical spectroscopies to reveal the presence of spectrally broad coupled electronic transitions with, at least partial, charge-transfer (CT) character. We monitor the CT state dynamics using tunable sub-20 fs pulses. We find that high photon energy excitation results in accelerated (sub-20 fs) CT formation times while activating pathways, which lead to long-lived (≫1 ns), possibly reactive CT species. On the other hand, visible light excitation results in a slower (≈45 fs) formation of bound CT states, which, however, recombine on the ultrafast sub-2 ps time scale.