Abstract
The ultrafast internal conversion (IC) dynamics of adonixanthin in organic solvents were studied by pump-supercontinuum probe (PSCP) and transient lens (TL) spectroscopy after photoexcitation to the S 2 state. Transient PSCP spectra in the range 344–768 nm provided the spectral evolution of the S 0 → S 2 ground state bleach and S 1 → S n excited state absorption. Time constants were τ 2 = 115 and 111 fs for the S 2 → S 1 IC and τ 1 = 6.4 and 5.8 ps for the S 1 → S 0 IC in acetone and methanol, respectively. There was only an insignificant polarity dependence of τ 1, underlining the negligible importance of intramolecular charge transfer (ICT) in the lowest-lying excited state of C 40 carotenoids with carbonyl substitution on the β-ionone ring. A blueshift and a spectral narrowing of the S 1 → S n ESA band, likely due to solvation dynamics, and formation of the adonixanthin radial cation at high pump energies via resonant two-photon ionization were found.
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