Reactivity of the charge transfer excited state of sodium decatungstate at the nanosecond time scale

Literature Information

Publication Date 2000-03-01
DOI 10.1039/A908588B
Impact Factor 3.676
Authors

J. A. Delaire, C. Giannotti


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Abstract

Previous studies have put into evidence the key role of a charge transfer excited state, noted X, in the primary steps of laser photolysis of sodium decatungstate solutions. In this work, we report a thorough study of the reactivity of the X transient towards different organic and inorganic substrates in acetonitrile and in water. The bimolecular reaction between X and the substrates is shown to occur on the nanosecond time-scale, either by H atom or electron transfer, and leads to the formation of the reduced form Y of decatungstate.We find that H atom transfer reactions are ruled by Z–H (Z=C, N, O) binding energies and lead to Y formation quantum yields that may reach the X formation quantum yield, whereas electron transfer reactions are ruled by the substrates' oxidation potential (Marcus reorganisation energy λ=1.0–1.3 eV for aromatics in acetonitrile) and lead to Y formation quantum yields similar to that obtained in the pure solvent.

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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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