Electrochemical concerted proton and electron transfers. Potential-dependent rate constant, reorganization factors, proton tunneling and isotope effects

Journal of Electroanalytical Chemistry

Volumn 588, Issue 2, 2006, Pages 197-206

  Costentin, Cyrille ^a   Robert, Marc ^a   Savéant, Jean Michel ^a  

^a UNIVERSITÉ PARIS DIDEROT   (France)

Author keywords

Activation driving force realtionships; Concerted proton electron transfers; Isotope effects

Indexed keywords

CYCLIC VOLTAMMETRY; ELECTRODES; ELECTRON TRANSITIONS; MATHEMATICAL MODELS; PROTONS; RATE CONSTANTS;

ACTIVATION-DRIVING FORCE RELATIONSHIP; CONCERTED PROTON-ELECTRON TRANSFERS; ISOTOPE EFFECTS;

ELECTROCHEMISTRY;

EID: 33644601917     PISSN: 15726657     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.jelechem.2005.12.027     Document Type: Article

References (47)

1. We take reductions as example in the following analysis. Transposition to oxidations is straightforward.
2. J.-M. Savéant T.T. Tidwell Advances in Physical Organic Chemistry vol. 35 2000 Academic Press New York 117 192
3. For recent reviews see 3b-e.
4. C.J. Chang, M.C.Y. Chang, N.H. Damrauer, and D.G. Nocera Biophys. Biochim. Acta 1655 2004 13
5. S. Hammes-Schiffer, and I. Nedialka Biophys. Biochim. Acta 1655 2004 29
6. J.M. Mayer, and I.J. Rhile Biophys. Biochim. Acta 1655 2004 51
7. R.I Cukier, and D.G. Nocera Annu. Rev. Phys. Chem. 49 1998 337
8. A.M. Kuznetsov, and J. Ulstrup Elektrokhimyia 39 2003 11
9. S.C. Weatherly, I.V. Yang, P.M. Armistead, and H.H. Thorp J. Phys. Chem. B 107 2003 372
10. M. Sjödin, S. Styring, H. Wolpher, Y. Xu, S. Sun, and L. Hammarström J. Am. Chem. Soc. 127 2005 3855
11. C. Costentin, D.H. Evans, M. Robert, J.-M. Savéant, and P.S. Singh J. Am. Chem. Soc. 127 2005 12490
12. H.O. Finklea, and R.M. Haddox J. Phys. Chem. B 108 2004 1694
13. M.W. Lehman, and D.H. Evans J. Phys. Chem. B 105 2001 8877
14. A. Soudackov, and S. Hammes-Schiffer J. Chem. Phys. 111 1999 4672
15. E. Hatcher, A. Soudackov, and S. Hammes-Schiffer J. Am. Chem. Soc. 126 2004 5763
16. R.I. Cukier J. Phys. Chem. 100 1996 15428
17. M.J. Knapp, K. Rickert, and J.P. Klinman J. Am. Chem. Soc. 124 2002 3865
18. A. Soudackov, and S. Hammes-Schiffer J. Am. Chem. Soc. 121 1999 5763
19. N. Iordanova, H. Decornez, and S. Hammes-Schiffer J. Am. Chem. Soc. 123 2001 5763
20. R.I. Cukier J. Phys. Chem. 99 1995 16101
21. See Ref. [12] for a discussion comparing this approach to the formal derivation of a more general CPET rate expression proposed in Ref. [8].
22. S. Hammes-Schiffer Acc. Chem. Res. 34 2001 273
23. A. Soudackov, and S. Hammes-Schiffer J. Chem. Phys. 111 2000 2385
24. A. Soudackov, E. Hatcher, and S. Hammes-Schiffer J. Chem. Phys. 122 2005 14505
25. R.A. Marcus P.A. Rock Special Topics in Electrochemistry 1977 Elsevier New York 151 179
26. V.G. Levich P. Delahay C.W. Tobias Advances in Electrochemistry and Electrochemical Engineering 1955 Wiley New York 250 371
27. S. Gosavi, and R.A. Marcus J. Phys Chem. B 104 2000 2057
28. R.A. Marcus, and N. Sutin N. Biophys. Biochim. Acta 811 1985 265
29. The expression given in Eq. 1 assumes that only transitions from reactant to product proton vibrational ground states are important. A more complete expression should take into account each pair of electron-proton states [10]. However, in the case of electrochemical CPET reactions, electronic levels are very close one to the other. An infinite number of electronic levels are considered, thus justifying the neglect of excited proton vibrational states.
30. L. Onsager J. Am. Chem. Soc. 58 1936 1486
31. P.M. Kiefer, and J.T. Hynes J. Phys. Chem. A 108 2004 11793
32. D. Borgis, and J.T. Hynes J. Phys. Chem. A 100 1996 1118
33. D. Borgis, and J.T. Hynes Chem. Phys. Lett. 170 1993 315
34. D. Borgis, S. Lee, and J.T. Hynes Chem. Phys. Lett. 162 1989 19
35. D. Borgis, and J.T. Hynes J. Chem. Phys. 94 1991 3619
36. S. Lee, and J.T. Hynes J. Chim. Phys. 93 1996 1783
37. C. Creutz, and N. Sutin J. Am. Chem. Soc. 110 1998 2418
38. This assumption has been verified on the water-superoxide ion system [5], which can be considered as an extreme case since the product complex is a dianion with an important repulsive electrostatic force within the complex.
39. Y. Georgievskii, and A.A. Stuchebrukhov J. Chem. Phys. 113 2000 10438
40. L. Landau Phys. Z. Sowjetunion 2 1932 46
41. C. Zener Proc. R. Soc. London, Ser. A 137 1932 696
42. B.S. Brunschwig, J. Logan, M.D. Newton, and N. Sutin J. Am. Chem. Soc. 102 1980 5798
43. W.H. Miller J. Phys. Chem. 83 1979 960
44. I.J. Rhile, and J.M. Mayer J. Am. Chem. Soc. 126 2004 12718
45. S.C. Weatherly, I.V. Yang, and H.H. Thorp J. Am. Chem. Soc. 123 2001 1236
46. D. Shukla, R.H. Young, and S. Farid J. Phys. Chem. A 108 2004 10386
47. N. Iordanova, and S. Hammes-Schiffer J. Am. Chem. Soc. 124 2002 4848