Direct spectroscopy of contact charge transfer states: Possible consequences for tryptophan excited-state deactivation pathways by O2 and formation of reactive oxygen species

Literature Information

Publication Date 2010-03-27
DOI 10.1039/B926289J
Impact Factor 3.676
Authors

Swen Siegert, Ferdinand Vogeler, Joachim Schiedt, Rainer Weinkauf


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Abstract

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 O2·stilbene, O2·indole and O2·N-methylindole the optical cross-sections of the conjugated chromophores are much larger than that of O2. This forces most of the anion-to-neutral photoexcitation into the CCT state. The CCT states lie below S1 for 2,2′-bithiophene·indole and O2·stilbene or even below T1 for O2·indole and O2·N-methylindole. Significant differences are found between the PD-PES of O2 with indole and N-methylindole indicating that different collision sites may have different CCT state energies and as a result different 1Δg 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 O2−·tryptophan+.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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