Free energy, entropy and volume of activation for electron transfer reactions in a polar solvent

Journal of Chemical Physics

Volumn 125, Issue 1, 2006, Pages

  Manjari, Swati R ^a   Kim, Hyung J ^a  

^a CARNEGIE MELLON UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CAVITY SIZE; ELECTRON TRANSFER (ET); POLAR SOLVENTS; TRANSITION STATES;

ACTIVATION ANALYSIS; CONTINUUM MECHANICS; ELECTRON TRANSPORT PROPERTIES; ENTROPY; FREE ENERGY; REACTION KINETICS;

ORGANIC SOLVENTS;

EID: 33745792339     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.2217941     Document Type: Article

References (40)

1. P. Finckh, H. Heitele, M. Volk, and M. E. Michel-Beyerle, J. Phys. Chem. 92, 6584 (1988);
2. H. Heitele, P. Finckh, S. Weeren, F. Pöllinger, and M. E. Michel-Beyerle, J. Phys. Chem. 93, 5173 (1989);
3. N. Liang, G. L. Closs, and J. R. Miller, J. Am. Chem. Soc. 111, 8740 (1989);
4. J. T. Hupp, G. A. Neyhart, T. J. Meyer, and E. M. Kober, J. Phys. Chem. 96, 10820 (1992);
5. T. Asahi, M. Ohkohchi, R. Matsusaka, N. Mataga, R. P. Zhang, A. Osuka, and K. Maruyama, J. Am. Chem. Soc. 115, 5665 (1993);
6. J. Kroon, H. Oevering, J. W. Verhoeven, J. M. Warman, A. M. Oliver, and M. N. Paddon-Row, J. Phys. Chem. 97, 5065 (1993);
7. A. Harriman, V. Heitz, and J.-P. Sauvage, J. Phys. Chem. 97, 5940 (1993).
8. J. Cortés, H. Heitele, and J. Jortner, J. Phys. Chem. 98, 2527 (1994).
9. C. M. Elliott, D. L. Derr, D. V. Matyushov, and M. D. Newton, J. Am. Chem. Soc. 120, 11714 (1998).
10. D. L. Derr and C. M. Elliott, J. Phys. Chem. 103, 7888 (1999).
11. P. Vath, M. B. Zimmt, D. V. Matyushov, and G. A. Voth, J. Phys. Chem. B 103, 9130 (1999);
12. P. Vath and M. B. Zimmt, J. Phys. Chem. A 104, 2626 (2000).
13. X. Zhao, J. A. Burt, F. J. Knorr, and J. L. McHale, J. Phys. Chem. A 105, 11110 (2001).
14. K. Kumar, I. V. Kurnikov, D. N. Beratan, D. H. Waldeck, and M. B. Zimmt, J. Phys. Chem. A 102, 5529 (1998);
15. I. Read, A. Napper, M. B. Zimmt, and D. H. Waldeck, J. Phys. Chem. A 104, 9385 (2000).
16. D. V. Matyushov, Chem. Phys. 174, 199 (1993);
17. Mol. Phys. 79, 795 (1993);
18. D. V. Matyushov and R. Schmid, J. Phys. Chem. 98, 5152 (1994).
19. R. A. Marcus, J. Chem. Phys. 24, 966, 979 (1956).
20. S. R. Manjari and H. J. Kim, J. Phys. Chem. B 110, 494 (2006).
21. S. R. Manjari and H. J. Kim, J. Chem. Phys. 123, 014504 (2005).
22. Solvent electronic polarization is assumed to be always at equilibrium because of its fast response.
23. A theoretical formulation of cavity size fluctuations in polar and nonpolar solvents similar to Eq. (1) was first developed in H. J. Kim, J. Chem. Phys. 105, 6818 (1996).
24. (a) Fluctuations of cavity size and its variation with the ET transition state were first pointed out by R. R. Dogonadze and A. M. Kuznetsov, in Comprehensive Treatise of Electrochemistry, Vol. 7, edited by B. E. Conway, J. O'M. Bockris, E. Yeager, S. U. M. Kahn, and R. E. White (Plenum, New York, 1983)
25. and later by A. M. Kuznetsov, Charge Transfer in Chemical Reaction Kinetics (Presses polytechniques universitaires et romandes, Lausanne, 1997).
26. (b) Influence of cavity fluctuations on free energetics and dynamics of adiabatic ET and its transition state structure was analyzed explicitly by J. Jeon and H. J. Kim [J. Chem. Phys. 106, 5979 (1997)] via the earlier theoretical formulation of Ref. 13.
27. R. C. Tolman, J. Chem. Phys. 17, 118, 333 (1949).
28. T. Kakitani and N. Mataga, J. Phys. Chem. 91, 6277 (1987);
29. E. A. Carter and J. T. Hynes, J. Phys. Chem. 93, 2184 (1989);
30. M. Tachiya, J. Phys. Chem. 93, 7050 (1989);
31. G. King and A. Warshel, J. Chem. Phys. 93, 8682 (1990);
32. Y.-P. Liu and M. D. Newton, J. Phys. Chem. 99, 12382 (1995);
33. T. Ichiye, J. Chem. Phys. 104, 7561 (1996);
34. R. B. Yelle and T. Ichiye, J. Phys. Chem. B 101, 4127 (1997).
35. T. Morita, B. M. Ladanyi, and J. T. Hynes, J. Phys. Chem. 93, 1386 (1989).
36. J. M. Malin, D. A. Ryan, and T. V. O'Halloran, J. Am. Chem. Soc. 100, 2097 (1978).
37. A. P. Szecsy and A. Haim, J. Am. Chem. Soc. 104, 3063 (1982).
38. A. Neves, W. Herrmann, and K. Wieghardt, Inorg. Chem. 23, 3435 (1984).
39. M. Martinez, M.-A. Pitarque, and R. van Eldik, Inorg. Chim. Acta 256, 51 (1997).
40. P. V. Bernhardt, F. Bozoglian, B. P. Macpherson, M. Martínez, G. Gonzalez, and B. Sienra, Eur. J. Inorg. Chem.2512 (2003).