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Theoretical Insights in ECL

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Luminescence in Electrochemistry

Abstract

ECL reaction mechanisms involved in all experimental approaches are characterized by a sequence of very fast second-order reactions taking place in the diffusion layer between transient species that, according to the exact process of ECL generation, may be generated at a single electrode, a pair of electrodes (anode-cathode), or through electron transfers between activated reactants and co-reactants. These extremely fast second-order reactions generate the extremely short-lived electronically excited state species, S*, which are deactivated through a rapid first-order emissive decay giving rise to the emission of light. These crucial species are therefore always generated and consumed within a narrow layer of solution of very small size compared to diffusion layers. Moreover, they are present within this layer at vanishingly small concentrations. This creates kinetic situations termed “reaction fronts” exact numerical treatment of which is almost impossible by classical numerical approaches. This chapter presents a series of numerical approaches based on the concepts developed by the authors to circumvent these severe complications and allow a precise and fast simulation of ECL reaction mechanisms. These are illustrated taking advantage of experimental examples featuring each main method of ECL generation.

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Acknowledgements

This work was supported by CNRS UMR8640 PASTEUR (CNRS, ENS and UPMC) and the French Ministry of Research and Higher Education as well as by ANR Chaires d’excellence (CHEX) 2010, ANR-10-CHEX-0012, MicroNanoChem.

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Authors and Affiliations

  1. Departement de Chimie, CNRS UMR 8640 PASTEUR, Ecole Normale Superieure-PSL Research University, Sorbonne Universites-UPMC Paris 6, CNRS, 24 rue Lhomond, 75005, Paris, France

    Alexander Oleinick, Oleksiy V. Klymenko, Irina Svir & Christian Amatore

  2. Department of Chemical and Process Engineering, University of Surrey, Guildford, GU2 7XH, UK

    Oleksiy V. Klymenko

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  1. Alexander Oleinick
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  2. Oleksiy V. Klymenko
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  3. Irina Svir
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  4. Christian Amatore
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Corresponding authors

Correspondence to Irina Svir or Christian Amatore .

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Editors and Affiliations

  1. Ecole Normale Superiecure de Cachan, PPSM, Cedex, France

    Fabien Miomandre

  2. Ecole Normale Superieure de Cachan, PPSM, Cachan, France

    Pierre Audebert

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Oleinick, A., Klymenko, O.V., Svir, I., Amatore, C. (2017). Theoretical Insights in ECL. In: Miomandre, F., Audebert, P. (eds) Luminescence in Electrochemistry. Springer, Cham. https://doi.org/10.1007/978-3-319-49137-0_7

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