Quenching of Singlet Oxygen by Carotenoids via Ultrafast Superexchange Dynamics

We analyze the quenching mechanism of singlet molecular oxygen (¹O₂) by carotenoids, namely lycopene, β-carotene, astaxanthin, and lutein, by means of quantum dynamics calculations and ab initio calculations. The singlet carotenoid (¹Car) and ¹O₂ molecules can form a weakly bound complex via donation of electron density from the highest occupied molecular orbital (HOMO) of the carotenoid to the π_g* orbitals of ¹O₂. The Dexter-type superexchange via charge transfer states (Car^•+/O₂^•–) governs the ¹O₂ quenching. The Car^•+/O₂^•– states are substantially higher in energy (2–4 eV) than the initial ¹Car/¹O₂ states. The quantum dynamics calculations indicate an ultrafast ¹O₂ quenching on a timescale of subpicosecond owing to the strong electronic couplings in the carotenoid/O₂ complexes. The superexchange mechanism via the Car^•+/O₂^•– states dominates the ¹O₂ quenching, although the direct two-electron coupling can also play a certain role.