Electron Tunneling Across Hexadecanethiolate Monolayers on Mercury Electrodes: Reorganization Energy, Structure, and Permeability of the Alkane/Water Interface

Journal of Physical Chemistry B

Volumn 103, Issue 40, 1999, Pages 8544-8551

  Slowinski, Krzysztof ^a   Slowinska, Katarzyna U ^a   Majda, Marcin ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001748488     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp991466a     Document Type: Article

References (59)

1. Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13248.
2. Farver, O.; Pecht, I. J. Biol. Inorg. Chem. 1997, 2, 387.
3. Beratan, D. N.; Skourtis, S. S. Curr. Opinion Chem. Biol. 1998, 2, 235.
4. Boxer, S. G. Annu. Rev. Biophys. Biophys. Chem. 1990, 19, 267.
5. Moser, C. C.; Page, C. C.; Fand, R.; Dutton, P. L. J. Bioenerg. Biomembr. 1995, 27, 263.
6. Bendall, D. S., Ed. Protein Electron Transfer; BIOS Scientific Publishers Ltd.: Oxford, 1996.
7. Structure and Bonding: Long-Range Electron Transfer in Biology; Springer-Verlag: New York, 1991; Vol. 75.
8. Curry, W. B.; Grabe, M. D.; Kurnikov, I. V.; Skourtis, S. S.; Beratan, D. N.; Regan, J. J.; Aquino, A. J. A.; Beroza, P.; Onuchic, J. G. J. Bioenerg. Biomembr. 1995, 27, 285.
9. Gray, H. B.; Winkler, J. R. Annu. Rev. Biochem. 1996, 65, 537.
10. Grabert, H.; Devoret, M. H. In Single Charge Tunneling, Coulomb Blockade Phenomena in Nanostructures; Grabert, H., Devoret, M. H., Eds.; Plenum Press: New York, 1992.
11. Aviram, A., Ratner, M., Eds. Molecular Electronics: Science and Technology; Ann. NY. Acad. Sci., 1998; Vol. 852.
12. Jortner, J., Ratner, M., Eds. Molecular Electronics; IUPAC and Blackwell Science: Oxford, 1997.
13. Marcus, R. A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265.
14. Moser, C. C.; Keske, J. M.; Warncke, K.; Farid, R. S.; Dutton, P. L. Nature 1992, 355, 796.
15. Closs, G. L.; Miller, J. R. Science 1988, 240, 440.
16. Kuki, A. Electronic Tunneling Paths in Proteins. Structure and Bonding. Long-Range Electron Transfer in Biology; Springer-Verlag: Berlin, 1991; p 49-84.
17. Beratan, D. N.; Onuchic, J. N.; Winkler, J. R.; Gray, H. B. Science 1992, 258, 1740.
18. Wuttke, D. S.; Bjerrum, M. J.; Winkler, J. R.; Gray, H. B. Science 1992, 256, 1007.
19. Langen, R.; Chang, I.-J.; Germanas, J. P.; Richards, J. H.; Winkler, J. R.; Gray, H. B. Science 1995, 268, 1733.
20. de Rege, P. J. F.; Williams, S. A.; Therien, M. J. Science 1995, 269, 1409.
21. Finklea, H. O.; Liu, L.; Ravenscroft, M. S.; Punturi, S. J. Phys. Chem. 1996, 100, 18852.
22. Cheng, J.; Saghi-Szabo, G.; Tossell, J. A.; Miller, C. J. J. Am. Chem. Soc. 1996, 118, 680.
23. Slowinski, K.; Chamberlain, R. V.; Bilewicz, R.; Majda, M. J. Am. Chem. Soc. 1996, 118, 4709.
24. Slowinski, K.; Chamberlain, R. V.; Miller, C. J.; Majda, M. J. Am. Chem. Soc. 1997, 119, 11910.
25. Finklea, H. O. Electrochemistry of Organized Monolayers of Thiols and Related Molecules on Electrodes. Electroanalytical Chemistry; Bard, A. J., Rubinstein, I., Eds.; Marcel Dekker: New York, 1996; p 109-335.
26. Chidsey, C. E. D. Science 1991, 251, 919.
27. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y.-P. J. Phys. Chem. 1995, 99, 13141.
28. Becka, A. M.; Miller, C. J. J. Phys. Chem. 1992, 96, 2657.
29. Finklea, H. O.; Hanshew, D. D. J. Am. Chem. Soc. 1992, 114, 3113.
30. Weber, K.; Hockett, L.; Creager, S. J. Phys. Chem. B 1997, 101, 8286.
31. Dubois, L. H.; Nuzzo, R. G. Synthesis, Structure, and Properties of Model Organic Surfaces. Annu. Rev. Phys. Chem. 1992, 43, 437.
32. Sachs, S. B.; Dudek, S. P.; Hsung, R. P.; Sita, L. R.; Smalley, J. F.; Newton, M. D.; Feldberg, S. W.; Chidsey, C. E. D. J. Am. Chem. Soc. 1997, 119, 10563.
33. Creager, S.; Yu, C. J.; Bamdad, C.; O'Connor, S.; MacLean, T.; Lam, E.; Chong Y.; Olsen, G. T.; Luo, J.; Gozin, M.; Kayyem, J. F. J. Am. Chem. Soc. 1999, 121, 1059.
34. Demoz, A.; Harrison, D. J. Langmuir 1993, 9, 1046.
35. Bruckner-Lea, C.; Kimmel, R. J.; Janata, J.; Conroy, J. F. T.; Caldwell, K. Electrochim. Acta 1995, 40, 2897.
36. Muskal, N.; Turyan, J.; Mandler, D. J. Electroanal. Chem. 1996, 409, 131.
37. In these experiments, a micrometrically driven hanging mercury drop electrode was used. This device allows us to control the Hg drop size by increasing or decreasing the volume of the suspended drop with ca. 1% precision.
38. Miller, C.; Cuendet, C. P.; Gratzel, M. J. Phys. Chem. 1991, 95, 877.
39. Miller, C.; Gratzel, M. J. Phys. Chem. 1991, 95, 5225.
40. Terrettaz, S.; Becka, A. M.; Traub, M. J.; Fettinger, J. C.; Miller, C. J. J. Phys. Chem. 1995, 99, 11216.
41. Cheng, J.; Miller, C. J. J. Phys. Chem. B 1997, 101, 1058.
42. Miller, C. J. Heterogeneous Electron-Transfer Kinetics at Metallic Electrodes. In Physical Electrochemistry: Principles, Methods, and Applications; Rubinstein, I., Ed.; M. Dekker: New York, 1995; p 27-79.
43. Kemula, W.; Kublik, Z. Anal. Chim. Acta 1958, 18, 104.
44. Becucci, L.; Moncelli, M. R.; Guidelli, R. J. Electroanal Chem. 1996, 413, 187.
45. Buoninsegni, F. T.; Herrero, R.; Moncelli, M. R. J. Electroanal. Chem. 1998, 452, 33.
46. Magnussen, O. M.; Ocko, B. M.; Deutsch, M.; Regan, M. J.; Pershan, P. S.; Abernathy, D.; Gruebel, G.; Legrand, J.-F. Nature 1996, 384, 250.
47. Saji, T.; Maryuyama, Y.; Aoyagui, S. J. Electroanal. Chem. 1978, 86, 219.
48. Birkin, P. R.; Silva-Martinez, S. Anal. Chem. 1997, 69, 2055.
49. Macpherson, J. V.; Jones, C. E.; Unwin, P. R. J. Phys. Chem. B 1998, 102, 9891.
50. 2) Figure 2.
51. Bard, A. J.; Faulkner, L. R. Electrochemical Methods, Fundamentals and Applications; John Wiley & Sons: New York, 1980; Chapter 5.2, p 142.
52. Fan, F.-R. F.; Bard, A. J. Science 1997, 277, 1791.
53. Weber, K. S.; Creager, S. E. J. Electroanal. Chem. 1998, 458, 17.
54. Becka, A. M.; Miller, C. J. J. Phys. Chem. 1993, 97, 6233.
55. Equation 8 does not include the image charge effects since they are negligible for the purpose of the argument presented in the subsequent section in the text.
56. 4+ radius.
57. Since the monolayer films used by Miller and co-workers (ref 40) were hydroxy terminated, the difference between our hexadecanethiolate monolayer and their α,ω-hydroxytetradecanethiol monolayers is only one σ-bond. Thus, the correction we applied gives high estimates of the expected values. However, our previous measurements (ref 24) showed that the rates of electron tunneling across the hydroxy-terminated monolayer are actually somewhat higher than those measured at methyl terminated monolayers of the same number of carbon atoms. We also note that since Miller's data were obtained on gold electrode where the alkyl chains are tilted by ca. 30°, they are intrinsically higher than ours obtained on Hg (0° tilt angle), everything else being the same, due to a contribution to the total rate from a tunneling pathway involving chain-to-chain coupling. Thus, overall, the correction we used is reasonably accurate.
58. We demonstrated previously that the increase of an electron tunneling rate in case A is due to additional contribution to the tunneling from a pathway involving chain-to-chain coupling (see ref 24).
59. Sharp, K. A.; Madan, B. J. Phys. Chem. B 1997, 101, 4343.