Direct spectroscopy of contact charge transfer states: possible consequences for tryptophan excited-state deactivation pathways by O2 and formation of reactive oxygen species.
This paper demonstrates that photodetachment photoelectron spectroscopy (PD-PES) of non-covalently bound heteromolecular anion clusters allows direct access to neutral contact charge transfer (CCT) states. The 2,2'-bithiophene.indole cluster is investigated as a model system in such a way that both chromophores have similar optical excitation cross-sections and hence the PD-PES shows the signature of both molecules. For the complexes O(2).stilbene, O(2).indole and O(2).N-methylindole the optical cross-sections of the conjugated chromophores are much larger than that of O(2). This forces most of the anion-to-neutral photoexcitation into the CCT state. The CCT states lie below S(1) for 2,2'-bithiophene.indole and O(2).stilbene or even below T(1) for O(2).indole and O(2).N-methylindole. Significant differences are found between the PD-PES of O(2) with indole and N-methylindole indicating that different collision sites may have different CCT state energies and as a result different (1)Delta(g) oxygen formation efficiencies. We discuss the possible consequences of the energetics and the geometry changes for the excited-state deactivation of tryptophan via the CCT state O(2)(-).tryptophan(+).
Siegert
Swen
S
Institut für Physikalische Chemie I, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany.
Vogeler
Ferdinand
F
Schiedt
Joachim
J
Weinkauf
Rainer
R
D007211:Indoles / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D056951:Photoelectron Spectroscopy; D011789:Quantum Theory; D017382:Reactive Oxygen Species / Q000737:chemistry*; D013267:Stilbenes / Q000737:chemistry; D014364:Tryptophan / Q000737:chemistry*
D007211:Indoles; D017382:Reactive Oxygen Species; D013267:Stilbenes; D014364:Tryptophan; D010100:Oxygen