An informative subtlety of itemperature-jump or coulostatic responses for surface-attached species |
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| Authors: | John F Smalley Marshall D Newton Stephen W Feldberg |
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| Institution: | 1. Università degli Studi di Milano, Dipartimento di Chimica, via Golgi 19, 20133 Milano, Italy;2. SajTom Light Future, W??erów 37/1, 32-090 W??erów, Poland;3. CNR – Istituto di Scienze e Tecnologie Molecolari, Via C. Golgi 19, Milano 20133, Italy;4. INSTM, Consorzio Interuniversitario per la Scienza e Tecnologia dei Materiali, Via San Giusti 9, Firenze, Italy;1. A.E Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of the Russian Academy of Sciences, 8 Acad. Arbuzov str., Kazan 420088, Russian Federation;2. Kazan National Research Technological University, 68 Karl Marx str, Kazan 420088, Russian Federation;3. Kazan (Volga region) Federal University, 18 Kremlyovskaya str., Kazan 420088, Russian Federation;1. Faculty of Chemistry, Silesian University of Technology, Marcina Strzody 9 street, 44-100 Gliwice, Poland;2. Center of Polymer and Carbon Materials, Polish Academy of Science, 41-819 Zabrze, Poland;1. Department of Applied Geology, Universität Göttingen, Goldschmidtstraße 3, D-37077 Göttingen, Germany;2. Department of Chemistry, Faculty of Sciences, University of Douala, Cameroon;3. Comité Afro-européen, Avenue Léopold II, 41, 5000 Namur, Belgium;4. Kultur und Nachhaltige Entwicklung CDD e.V., Postfach 1502, D-37005 Göttingen, Germany;5. Department of Sedimentology & Environmental Geology, University of Göttingen, Goldschmidtstraße 3, D-37077 Göttingen, Germany |
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| Abstract: | Theoretical relationships are developed to describe the open-circuit responses associated with the indirect laser-induced temperature-jump (ILIT) method, a method for measuring fast electron-transfer rate constants of surface-attached redox species. The analysis is also applicable to data obtained using the coulostatic charge-injection method. The unique relationship between km, the relaxation rate constant for the ILIT (or coulostatic) response, and Ei, the potential at which the system is initially poised, exhibits a surprising sensitivity to the values of k0, Ei0′ (the standard rate constant and formal potential for the redox couple), α (the transfer coefficient in the Butler–Volmer equation) and γ (a dimensionless parameter which is directly proportional to the total surface concentration of the redox moiety). ILIT data for several examples of surface-attached ferrocene moieties confirm the theoretically predicted km vs Ei behavior. Values of Ei0′ and γ extracted from the ILIT data agree well with the values obtained from cyclic voltammetric data thereby confirming that the ILIT and cyclic voltammogram (CV) experiments are sampling the same ferrocene population. |
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| Keywords: | Temperature-jump Laser ILIT Coulostatic Surface-attached redox species Redox capacitance Electron transfer resistance |
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