Photoinduced electron transfer from excited [tris(2,2′-bipyridine)ruthenium(II)]2+ to a series of anthraquinones with small positive or negative Gibbs energy of reaction. Marcus behavior and negative activation enthalpies
文献信息
In the electron transfer (ET) quenching reactions of electronically excited *Ru(bpy)32+ in acetonitrile an increase of the rate constant kq is observed in the series of 2-methyl-, 1-chloro-, and 1-nitro-anthraquinone as quenchers. If alkali salts are used as supporting electrolytes the AQ- radical anions are found to form specific associates with the alkali cations. In the presence of non-associating tetraalkylammonium salts the system follows the predictions of Marcus theory. Numerical methods are developed which allow the determination of the rate constants of the conventional reaction scheme. This analysis shows that the quantum yield of free AQ- radical anion formation is governed by the interplay of forward, reverse and back ET. Negative activation enthalpies are found for the activation controlled quenching reactions. From the numerical analysis of the system of rate constants it is inferred that this phenomenon is due to the elementary ET step in the reaction sequence. We discuss the pre-equilibrium and elementary reaction models for reactions with negative activation enthalpy and present, to our knowledge, the first example of successful discrimination between them.
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Physical Chemistry Chemical Physics

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.














