How does the solvent control electron transfer? Experimental and theoretical studies of the simplest charge transfer reaction

Journal of Physical Chemistry B

Volumn 105, Issue 49, 2001, Pages 12230-12241

  Barthel, Erik R ^a   Martini, Ignacio B ^a   Schwartz, Benjamin J ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DIELECTRIC SOLVATION;

CHEMICAL RELAXATION; COMPUTER SIMULATION; DEGREES OF FREEDOM (MECHANICS); DIELECTRIC PROPERTIES; ELECTRON ENERGY LEVELS; ELECTRON TRANSITIONS; MOLECULAR DYNAMICS; NEGATIVE IONS; REACTION KINETICS; SODIUM; SOLVENTS; SPECTROSCOPIC ANALYSIS;

CHARGE TRANSFER;

EID: 0035857203     PISSN: 10895647     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp011150e     Document Type: Article

References (118)

1. For a recent review, see: Barbara, P.F.; Meyer, T.J.; Ratner, M.A. J. Phys. Chem. 1996, 100, 13148.
2. Marcus, R.A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265.
3. Marcus, R.A. J. Chem. Phys. 1956, 24, 966. Marcus, R.A. Annu. Rev. Phys, Chem. 1964, 15, 155.
4. Marcus, R.A. J. Chem. Phys. 1956, 24, 966. Marcus, R.A. Annu. Rev. Phys, Chem. 1964, 15, 155.
5. See, e.g, Closs, G.; Miller, J.R. Science, 1988, 240, 440. DeVault, D. Quantum Mechanical Tunneling in Biological Systems; Cambridge University Press: Cambridge, 1984.
6. See, e.g, Closs, G.; Miller, J.R. Science, 1988, 240, 440. DeVault, D. Quantum Mechanical Tunneling in Biological Systems; Cambridge University Press: Cambridge, 1984.
7. Kuharski, R.A.; Bader, J.S.; Chandler, D.; Sprik, M.; Klein, M.L.; Impey, R.W. J. Chem. Phys. 1988, 89, 3248. Bader, J.S.; Chandler, D. J. Phys. Chem. 1992, 96, 6423.
8. Kuharski, R.A.; Bader, J.S.; Chandler, D.; Sprik, M.; Klein, M.L.; Impey, R.W. J. Chem. Phys. 1988, 89, 3248. Bader, J.S.; Chandler, D. J. Phys. Chem. 1992, 96, 6423.
9. Jen, C.F.; Warshel, A. J. Phys. Chem. A 1999, 103, 11378.
10. Tran, V.; Schwartz, B.J. J. Phys. Chem. B 1999, 103, 5570.
11. Aherne, D.; Tran, V.; Schwartz, B.J. J. Phys. Chem. B 2000, 104, 5382.
12. For a review of CTTS phenomena, see Blandamer, M.J.; Fox, M.F. Chem. Rev. 1970, 70, 59.
13. See, e.g, Sexner, D.; Dessent, C.E.H.; Johnson, M.A. J. Chem. Phys. 1996, 105, 7231. Lehr. L.; Zanni, M.T.; Frischkorn, C.; Weinkauf, R.; Neumark, D.M. Science 1999, 284, 635.
14. See, e.g, Sexner, D.; Dessent, C.E.H.; Johnson, M.A. J. Chem. Phys. 1996, 105, 7231. Lehr. L.; Zanni, M.T.; Frischkorn, C.; Weinkauf, R.; Neumark, D.M. Science 1999, 284, 635.
15. Combariza, J.E.; Kestner, N.R.; Jortner, J. J. Chem. Phys. 1994, 101, 2851.
16. See, e.g., Jortner, J.; Ottolenghi, M.; Stein, G. J. Phys. Chem. 1964, 68, 247. Grossweiner, L.I.; Matheson, J. Phys. Chem. 1957, 61, 1089.
17. See, e.g., Jortner, J.; Ottolenghi, M.; Stein, G. J. Phys. Chem. 1964, 68, 247. Grossweiner, L.I.; Matheson, J. Phys. Chem. 1957, 61, 1089.
18. Sheu, W.-S.; Rossky, P.J. Chem. Phys. Lett. 1993, 202, 186; 1993, 213, 233; J. Phys. Chem. 1996, 100, 1295. Sheu, W.-S.; Rossky, P.J.; J. Am. Chem. Soc. 1993, 115, 7729.
19. Sheu, W.-S.; Rossky, P.J. Chem. Phys. Lett. 1993, 202, 186; 1993, 213, 233; J. Phys. Chem. 1996, 100, 1295. Sheu, W.-S.; Rossky, P.J.; J. Am. Chem. Soc. 1993, 115, 7729.
20. Sheu, W.-S.; Rossky, P.J. Chem. Phys. Lett. 1993, 202, 186; 1993, 213, 233; J. Phys. Chem. 1996, 100, 1295. Sheu, W.-S.; Rossky, P.J.; J. Am. Chem. Soc. 1993, 115, 7729.
21. Sheu, W.-S.; Rossky, P.J. Chem. Phys. Lett. 1993, 202, 186; 1993, 213, 233; J. Phys. Chem. 1996, 100, 1295. Sheu, W.-S.; Rossky, P.J.; J. Am. Chem. Soc. 1993, 115, 7729.
22. Staib, A.; Borgis, D. J. Chem. Phys. 1995, 103, 2642. Borgis, D.; Staib, A. Chem. Phys. Lett. 1994, 230, 405. Staib, A.; Borgis, D. J. Chem. Phys. 1996, 104, 9027; ibid. 1996, 104, 4776. Borgis, D.; Staib, A. Condens. Matt. 1996, 8, 9389.
23. Staib, A.; Borgis, D. J. Chem. Phys. 1995, 103, 2642. Borgis, D.; Staib, A. Chem. Phys. Lett. 1994, 230, 405. Staib, A.; Borgis, D. J. Chem. Phys. 1996, 104, 9027; ibid. 1996, 104, 4776. Borgis, D.; Staib, A. Condens. Matt. 1996, 8, 9389.
24. Staib, A.; Borgis, D. J. Chem. Phys. 1995, 103, 2642. Borgis, D.; Staib, A. Chem. Phys. Lett. 1994, 230, 405. Staib, A.; Borgis, D. J. Chem. Phys. 1996, 104, 9027; ibid. 1996, 104, 4776. Borgis, D.; Staib, A. Condens. Matt. 1996, 8, 9389.
25. Staib, A.; Borgis, D. J. Chem. Phys. 1995, 103, 2642. Borgis, D.; Staib, A. Chem. Phys. Lett. 1994, 230, 405. Staib, A.; Borgis, D. J. Chem. Phys. 1996, 104, 9027; ibid. 1996, 104, 4776. Borgis, D.; Staib, A. Condens. Matt. 1996, 8, 9389.
26. Staib, A.; Borgis, D. J. Chem. Phys. 1995, 103, 2642. Borgis, D.; Staib, A. Chem. Phys. Lett. 1994, 230, 405. Staib, A.; Borgis, D. J. Chem. Phys. 1996, 104, 9027; ibid. 1996, 104, 4776. Borgis, D.; Staib, A. Condens. Matt. 1996, 8, 9389.
27. Chen, H.Y.; Sheu, W.-S. J. Am. Chem. Soc. 2000, 122, 7534.
28. Fleming, G.R. Chemical Applications of Ultrafast Spectroscopy; Oxford University Press: New York, 1986.
29. Long, F.H.; Shi, X.; Lu, H.; Eisenthal, K.B. J. Phys. Chem. 1994, 98, 7252. Long, F.H.; Lu, H.; Shi, X.; Eisenthal, K.B. Chem. Phys. Lett. 1990, 169, 165. Long, F.H.; Lu, H.; Eisenthal, K.B. J. Chem. Phys. 1989, 91, 4413.
30. Long, F.H.; Shi, X.; Lu, H.; Eisenthal, K.B. J. Phys. Chem. 1994, 98, 7252. Long, F.H.; Lu, H.; Shi, X.; Eisenthal, K.B. Chem. Phys. Lett. 1990, 169, 165. Long, F.H.; Lu, H.; Eisenthal, K.B. J. Chem. Phys. 1989, 91, 4413.
31. Long, F.H.; Shi, X.; Lu, H.; Eisenthal, K.B. J. Phys. Chem. 1994, 98, 7252. Long, F.H.; Lu, H.; Shi, X.; Eisenthal, K.B. Chem. Phys. Lett. 1990, 169, 165. Long, F.H.; Lu, H.; Eisenthal, K.B. J. Chem. Phys. 1989, 91, 4413.
32. Gelabert, H.; Gauduel, Y. J. Phys. Chem. 1996, 100, 13993. Gauduel, Y.; Gelabert, H.; Ashokkumar, M. Chem. Phys. 1995, 197, 167. Gauduel, Y.; Pommeret, S.; Migus, A.; Yamada, N.; Antonetti, A. J. Opt. Soc. Am. B 1990, 7, 1528.
33. Gelabert, H.; Gauduel, Y. J. Phys. Chem. 1996, 100, 13993. Gauduel, Y.; Gelabert, H.; Ashokkumar, M. Chem. Phys. 1995, 197, 167. Gauduel, Y.; Pommeret, S.; Migus, A.; Yamada, N.; Antonetti, A. J. Opt. Soc. Am. B 1990, 7, 1528.
34. Gelabert, H.; Gauduel, Y. J. Phys. Chem. 1996, 100, 13993. Gauduel, Y.; Gelabert, H.; Ashokkumar, M. Chem. Phys. 1995, 197, 167. Gauduel, Y.; Pommeret, S.; Migus, A.; Yamada, N.; Antonetti, A. J. Opt. Soc. Am. B 1990, 7, 1528.
35. Assel, M.; Laenen, R.; Laubereau, A. Chem. Phys. Lett. 1998, 289, 267.
36. Kloepfer, J.A.; Vilchiz, V.H.; Lenchenkov, V.H.; Bradforth, S.E. Chem. Phys. Lett. 1998, 298, 120. Kloepfer, J.A.; Vilchiz, V.H.; Lenchenkov, V.A.; Germaine, A.C.; Bradforth, S.E. J. Chem. Phys. 2000, 113, 6288.
37. Kloepfer, J.A.; Vilchiz, V.H.; Lenchenkov, V.H.; Bradforth, S.E. Chem. Phys. Lett. 1998, 298, 120. Kloepfer, J.A.; Vilchiz, V.H.; Lenchenkov, V.A.; Germaine, A.C.; Bradforth, S.E. J. Chem. Phys. 2000, 113, 6288.
38. Jimenez, R.; Fleming, G.R.; Kumar, P.V.; Maroncelli, M. Nature 1994, 369, 471.
39. See, e.g, Zolotov, B.; Gan, A.; Fainberg, B.D.; Huppert, D. J. Lumin. 1997, 72, 842. Zolotov, B.; Gan, A.; Fainberg, B.D.; Huppert, D. Chem. Phys. Lett. 1997, 265, 418. Winkler, K.; Lindner, J.; Bursing, H.; Vohringer, P. J. Chem. Phys. 2000, 113, 4674. Castner, E.W.; Chang, Y. J.; Chu, Y.C.; Walrafen, G.E. J. Chem. Phys. 1995, 102, 653.
40. See, e.g, Zolotov, B.; Gan, A.; Fainberg, B.D.; Huppert, D. J. Lumin. 1997, 72, 842. Zolotov, B.; Gan, A.; Fainberg, B.D.; Huppert, D. Chem. Phys. Lett. 1997, 265, 418. Winkler, K.; Lindner, J.; Bursing, H.; Vohringer, P. J. Chem. Phys. 2000, 113, 4674. Castner, E.W.; Chang, Y. J.; Chu, Y.C.; Walrafen, G.E. J. Chem. Phys. 1995, 102, 653.
41. See, e.g, Zolotov, B.; Gan, A.; Fainberg, B.D.; Huppert, D. J. Lumin. 1997, 72, 842. Zolotov, B.; Gan, A.; Fainberg, B.D.; Huppert, D. Chem. Phys. Lett. 1997, 265, 418. Winkler, K.; Lindner, J.; Bursing, H.; Vohringer, P. J. Chem. Phys. 2000, 113, 4674. Castner, E.W.; Chang, Y. J.; Chu, Y.C.; Walrafen, G.E. J. Chem. Phys. 1995, 102, 653.
42. See, e.g, Zolotov, B.; Gan, A.; Fainberg, B.D.; Huppert, D.J. Lumin. 1997, 72, 842. Zolotov, B.; Gan, A.; Fainberg, B.D.; Huppert, D. Chem. Phys. Lett. 1997, 265, 418. Winkler, K.; Lindner, J.; Bursing, H.; Vohringer, P. J. Chem. Phys. 2000, 113, 4674. Castner, E.W.; Chang, Y.J.; Chu, Y.C.; Walrafen, G.E. J. Chem. Phys. 1995, 102, 653.
43. Barthel, E.R.; Martini, I.B.; Schwartz, B.J. J. Chem. Phys. 2000, 112, 9433.
44. Martini, I.B.; Barthel, E.R.; Schwartz, B.J. J. Chem. Phys. 2000, 113, 11245.
45. For reviews on alkali metal anion solutions, see: Dye, J.L. J. Phys. IV 1992, 1, 259. Dye, J.L. Prog. Inorg. Chem. 1984, 32, 327. Dye, J.L. J. Chem. Educ. 1977, 6, 332.
46. For reviews on alkali metal anion solutions, see: Dye, J.L. J. Phys. IV 1992, 1, 259. Dye, J.L. Prog. Inorg. Chem. 1984, 32, 327. Dye, J.L. J. Chem. Educ. 1977, 6, 332.
47. For reviews on alkali metal anion solutions, see: Dye, J.L. J. Phys. IV 1992, 1, 259. Dye, J.L. Prog. Inorg. Chem. 1984, 32, 327. Dye, J.L. J. Chem. Educ. 1977, 6, 332.
48. 0 species was provided by John Miller. See also: Piotrowiak, P.; Miller, J.R. J. Am. Chem. Soc. 1991, 113, 5086. Bockrath, B.; Dorfman, L.M. J. Phys. Chem. 1975, 79, 1509; 1973, 77, 1002.
49. 0 species was provided by John Miller. See also: Piotrowiak, P.; Miller, J.R. J. Am. Chem. Soc. 1991, 113, 5086. Bockrath, B.; Dorfman, L.M. J. Phys. Chem. 1975, 79, 1509; 1973, 77, 1002.
50. 0 species was provided by John Miller. See also: Piotrowiak, P.; Miller, J.R. J. Am. Chem. Soc. 1991, 113, 5086. Bockrath, B.; Dorfman, L.M. J. Phys. Chem. 1975, 79, 1509; 1973, 77, 1002.
51. Dorfman, L.M.; Jou, F.Y.; Wageman, R. Ber. Bunsen-Ges. Phys. Chem. 1971, 75, 681. Jou, F.Y.; Freeman, G.R. Can. J. Phys. 1976, 54, 3693.
52. Dorfman, L.M.; Jou, F.Y.; Wageman, R. Ber. Bunsen-Ges. Phys. Chem. 1971, 75, 681. Jou, F.Y.; Freeman, G.R. Can. J. Phys. 1976, 54, 3693.
53. Takasu, R.; Ito, H.; Nishikawa, K.; Hashimoto, K.; Okuda, R.; Fuke, K. J. Elec. Spec. Relat. Phenom. 2000, 106, 127. Takasu, R.; Misaizu, F.; Hashimoto, K.; Fuke, K. J. Phys. Chem. A 1997, 101, 3078. Hashimoto, K.; Kamimoto, T.; Fuke, K. Chem. Phys. Lett. 1997, 266, 7.
54. Takasu, R.; Ito, H.; Nishikawa, K.; Hashimoto, K.; Okuda, R.; Fuke, K. J. Elec. Spec. Relat. Phenom. 2000, 106, 127. Takasu, R.; Misaizu, F.; Hashimoto, K.; Fuke, K. J. Phys. Chem. A 1997, 101, 3078. Hashimoto, K.; Kamimoto, T.; Fuke, K. Chem. Phys. Lett. 1997, 266, 7.
55. Takasu, R.; Ito, H.; Nishikawa, K.; Hashimoto, K.; Okuda, R.; Fuke, K. J. Elec. Spec. Relat. Phenom. 2000, 106, 127. Takasu, R.; Misaizu, F.; Hashimoto, K.; Fuke, K. J. Phys. Chem. A 1997, 101, 3078. Hashimoto, K.; Kamimoto, T.; Fuke, K. Chem. Phys. Lett. 1997, 266, 7.
56. Chandler, D. Introduction to Modern Statistical Mechanics; Oxford University Press: New York, 1987.
57. See, e.g., Georgievskii, Y.; Hsu, C.-P.; Marcus, R.A. J. Chem. Phys. 1999, 110, 5307.
58. For review articles, see: Rossky, P.J.; Simon, J.D. Nature 1994, 370, 263. Maroncelli, M. J. Mol. Liq. 1993, 57, 1. Cho, M.; Fleming, G.R. Annu. Rev. Phys. Chem. 1996, 47, 109. Maroncelli, M.; MacInnis, J.; Fleming, G.R. Science 1989, 243, 1674.
59. For review articles, see: Rossky, P.J.; Simon, J.D. Nature 1994, 370, 263. Maroncelli, M. J. Mol. Liq. 1993, 57, 1. Cho, M.; Fleming, G.R. Annu. Rev. Phys. Chem. 1996, 47, 109. Maroncelli, M.; MacInnis, J.; Fleming, G.R. Science 1989, 243, 1674.
60. For review articles, see: Rossky, P.J.; Simon, J.D. Nature 1994, 370, 263. Maroncelli, M. J. Mol. Liq. 1993, 57, 1. Cho, M.; Fleming, G.R. Annu. Rev. Phys. Chem. 1996, 47, 109. Maroncelli, M.; MacInnis, J.; Fleming, G.R. Science 1989, 243, 1674.
61. For review articles, see: Rossky, P.J.; Simon, J.D. Nature 1994, 370, 263. Maroncelli, M. J. Mol. Liq. 1993, 57, 1. Cho, M.; Fleming, G.R. Annu. Rev. Phys. Chem. 1996, 47, 109. Maroncelli, M.; MacInnis, J.; Fleming, G.R. Science 1989, 243, 1674.
62. See, e.g., Song, X.Y.; Chandler, D.; J. Chem. Phys. 1998, 108, 2594. Hsu, C.-P.; Song, X.Y.; Marcus, R.A. J. Phys. Chem. B 1997, 101, 2456, Ravichandran, S.; Roy, S.; Bagchi, B. J. Phys. Chem. 1995, 99, 2489. Calef, D.F.; Wolynes, P.G. J. Phys. Chem. 1983, 87, 3387;.
63. See, e.g., Song, X.Y.; Chandler, D.; J. Chem. Phys. 1998, 108, 2594. Hsu, C.-P.; Song, X.Y.; Marcus, R.A. J. Phys. Chem. B 1997, 101, 2456, Ravichandran, S.; Roy, S.; Bagchi, B. J. Phys. Chem. 1995, 99, 2489. Calef, D.F.; Wolynes, P.G. J. Phys. Chem. 1983, 87, 3387;.
64. See, e.g., Song, X.Y.; Chandler, D.; J. Chem. Phys. 1998, 108, 2594. Hsu, C.-P.; Song, X.Y.; Marcus, R.A. J. Phys. Chem. B 1997, 101, 2456, Ravichandran, S.; Roy, S.; Bagchi, B. J. Phys. Chem. 1995, 99, 2489. Calef, D.F.; Wolynes, P.G. J. Phys. Chem. 1983, 87, 3387;.
65. See, e.g., Song, X.Y.; Chandler, D.; J. Chem. Phys. 1998, 108, 2594. Hsu, C.-P.; Song, X.Y.; Marcus, R.A. J. Phys. Chem. B 1997, 101, 2456, Ravichandran, S.; Roy, S.; Bagchi, B. J. Phys. Chem. 1995, 99, 2489. Calef, D.F.; Wolynes, P.G. J. Phys. Chem. 1983, 87, 3387.
66. For simulation studies on solvation following the photoexcitation and size change of the hydrated electron, see: Schwartz, B.J.; Rossky, P.J. J. Mol. Liq. 1995, 65-6, 23. Schwartz, B.J.; Rossky, P.J. J. Chem. Phys. 1996, 105, 6997.
67. For simulation studies on solvation following the photoexcitation and size change of the hydrated electron, see: Schwartz, B.J.; Rossky, P.J. J. Mol. Liq. 1995, 65-6, 23. Schwartz, B.J.; Rossky, P.J. J. Chem. Phys. 1996, 105, 6997.
68. Other simulations involving solvation of a solute size change include: Ando, K.; Karo, S. J. Chem. Phys. 1991, 95, 5966. Herman, M.F.; Berne, B.J. J. Chem. Phys. 1983, 78, 4103. Yamaguchi, T.; Kimura, T.; Hirota, N. J. Chem. Phys. 1999, 111, 4169. Stephens, M.D.; Saven, J.G.; Skinner, J.L. J. Chem. Phys. 1997, 106, 2129. Phelps, D.; Weaver, M.J.; Ladanyi, B.M. Chem. Phys. 1993, 176, 575.
69. Other simulations involving solvation of a solute size change include: Ando, K.; Karo, S. J. Chem. Phys. 1991, 95, 5966. Herman, M.F.; Berne, B.J. J. Chem. Phys. 1983, 78, 4103. Yamaguchi, T.; Kimura, T.; Hirota, N. J. Chem. Phys. 1999, 111, 4169. Stephens, M.D.; Saven, J.G.; Skinner, J.L. J. Chem. Phys. 1997, 106, 2129. Phelps, D.; Weaver, M.J.; Ladanyi, B.M. Chem. Phys. 1993, 176, 575.
70. Other simulations involving solvation of a solute size change include: Ando, K.; Karo, S. J. Chem. Phys. 1991, 95, 5966. Herman, M.F.; Berne, B.J. J. Chem. Phys. 1983, 78, 4103. Yamaguchi, T.; Kimura, T.; Hirota, N. J. Chem. Phys. 1999, 111, 4169. Stephens, M.D.; Saven, J.G.; Skinner, J.L. J. Chem. Phys. 1997, 106, 2129. Phelps, D.; Weaver, M.J.; Ladanyi, B.M. Chem. Phys. 1993, 176, 575.
71. Other simulations involving solvation of a solute size change include: Ando, K.; Karo, S. J. Chem. Phys. 1991, 95, 5966. Herman, M.F.; Berne, B.J. J. Chem. Phys. 1983, 78, 4103. Yamaguchi, T.; Kimura, T.; Hirota, N. J. Chem. Phys. 1999, 111, 4169. Stephens, M.D.; Saven, J.G.; Skinner, J.L. J. Chem. Phys. 1997, 106, 2129. Phelps, D.; Weaver, M.J.; Ladanyi, B.M. Chem. Phys. 1993, 176, 575.
72. Other simulations involving solvation of a solute size change include: Ando, K.; Karo, S. J. Chem. Phys. 1991, 95, 5966. Herman, M.F.; Berne, B.J. J. Chem. Phys. 1983, 78, 4103. Yamaguchi, T.; Kimura, T.; Hirota, N. J. Chem. Phys. 1999, 111, 4169. Stephens, M.D.; Saven, J.G.; Skinner, J.L. J. Chem. Phys. 1997, 106, 2129. Phelps, D.; Weaver, M.J.; Ladanyi, B.M. Chem. Phys. 1993, 176, 575.
73. For a theoretical analysis of nonpolar solvation based on instantaneous normal modes, see: Ladanyi, B.M.; Stratt, R.M. J. Phys. Chem. 1996, 100, 1266. A theoretical analysis of nonpolar solvation in terms of viscoelastic continuum theory can be found in: Berg, M. J. Phys. Chem. A 1998, 102, 17.
74. For a theoretical analysis of nonpolar solvation based on instantaneous normal modes, see: Ladanyi, B.M.; Stratt, R.M. J. Phys. Chem. 1996, 100, 1266. A theoretical analysis of nonpolar solvation in terms of viscoelastic continuum theory can be found in: Berg, M. J. Phys. Chem. A 1998, 102, 17.
75. For experimental work on nonpolar solvation, see, e.g.: Ma, J.; Vanden Bout, D.; Berg, M. J. Chem. Phys. 1995, 103, 9146. Wendt, H.; Richert, R. J. Phys. Chem. A 1998, 102, 5775.
76. For experimental work on nonpolar solvation, see, e.g.: Ma, J.; Vanden Bout, D.; Berg, M. J. Chem. Phys. 1995, 103, 9146. Wendt, H.; Richert, R. J. Phys. Chem. A 1998, 102, 5775.
77. The experimentally measured solvent response functions of THF and many other liquids are tabulated in: Reynolds, L.; Gardecki, J.A.; Frankland, S.J.V.; Horng, M.L.; Maroncelli, M. J. Phys. Chem. 1996, 100, 10337.
78. Vath, P.; Zimmt, M.B.; Matyushov, D.V.; Voth, G.A. J. Phys. Chem. B 1999, 103, 9130.
79. See, e.g., Nowak, R.; Bernstein, E.R. J. Phys. Chem. 1987, 86, 4783 as well as ref 36.
80. The fact that atomic species change undergo size changes of this magnitude when changing their oxidation state is obvious from standard tables of ionic and van der Waals radii. See, for example: Huheey, J.E. Inorganic Chemistry, 3rd ed.; Harper & Row: New York, 1983.
81. Toukan, K.; Rahman, A. Phys. Rev. B 1985, 31, 2643.
82. The actual equilibria are somewhat more complex than depicted in eq 3 and involve solvated electrons as well as metal cations and anions; see ref 25 for details.
83. See, e.g.: Matalon, S.; Golden, S.; Ottolenghi, M. J. Phys. Chem. 1969, 73, 3098. Lok, M.T.; Tehan, F.J.; Dye, J.L. J. Phys. Chem. 1972, 76, 2975.
84. See, e.g.: Matalon, S.; Golden, S.; Ottolenghi, M. J. Phys. Chem. 1969, 73, 3098. Lok, M.T.; Tehan, F.J.; Dye, J.L. J. Phys. Chem. 1972, 76, 2975.
85. Lok, M.T.; Tehan, F.J.; Dye, J.L. J. Phys. Chem. 1972, 76, 2975.
86. Early flash photolysis work on alkali metal anions can be found in: Huppert, D.; Rentzepis, P.M.; Struve, W.S. J. Phys. Chem. 1975, 79, 2850. Huppert, D.; Rentzepis, P.M. J. Phys. Chem. 1976, 64, 191. Kloosterboer, J.G.; Giling, L.J.; Rettschnick, R.P.H.; Van Voorst, J.D.W. Chem. Phys. Lett. 1971, 8, 462.
87. Early flash photolysis work on alkali metal anions can be found in: Huppert, D.; Rentzepis, P.M.; Struve, W.S. J. Phys. Chem. 1975, 79, 2850. Huppert, D.; Rentzepis, P.M. J. Phys. Chem. 1976, 64, 191. Kloosterboer, J.G.; Giling, L.J.; Rettschnick, R.P.H.; Van Voorst, J.D.W. Chem. Phys. Lett. 1971, 8, 462.
88. Early flash photolysis work on alkali metal anions can be found in: Huppert, D.; Rentzepis, P.M.; Struve, W.S. J. Phys. Chem. 1975, 79, 2850. Huppert, D.; Rentzepis, P.M. J. Phys. Chem. 1976, 64, 191. Kloosterboer, J.G.; Giling, L.J.; Rettschnick, R.P.H.; Van Voorst, J.D.W. Chem. Phys. Lett. 1971, 8, 462.
89. Seddon, W.A.; Fletcher, J.W. J. Phys. Chem. 1980, 84, 1104.
90. Dye, J.L. J. Phys. Chem. 1980, 84, 1084.
91. There is some difference of opinion in the literature about how to identify the neutral alkali metal species in solution. One possibility is that this species is an ion pair between a solvated electron and an alkali metal cation. In refs 23 and 24, however, we have argued that the transient spectroscopy of these systems show no dynamics that could be associated with a second electron detaching from the metal anion, identifying the neutral species as a genuine solvated metal atom.
92. - 3s electrons into the CTTS excited state. The core atom is shielded from the solvent by the excited, Rydberg-like CTTS electron and, thus, has a 590 nm absorption similar to that in the gas phase (the famous Na "D" line). It is not until the CTTS electron detaches and the atom is solvated that the spectrum becomes that shown by the dashed curve in Figure 4.
93. 2*p in the new model.
94. 0. Even if the known cross-section of the solvated electron is nor included in the delayed ejection model, the omission does not alter the quality of the fit seen in Figure 6.
95. Bradforth. S.E. Private communication. 2001.
96. Vilchiz, V.H.; Kloepfer, J.A.; Germaine, A.C.; Lenchenkov, V.A.; Bradforth, S.E. J. Phys. Chem. A 2001. 105, 1711.
97. Wang, Z.: Shoshana, O.: Ruhman, S. Proceedings of the 12th International Conference on Ultrafast Phenomena; Springer Series in Chemical Physics 66; Springer-Verlag: Berlin, 2001. Wang, Z.; Shoshana, O.; Ruhman, S. J. Chem. Phys., submitted.
98. Polarized hole-burning provides the possibility of spectrally separating multiple electronic transitions with orthogonally oriented transition dipoles, as has been done experimentally for the permanganate anion (Yu, J.W.; Berg, M. J. Phys. Chem. 1993, 97, 1758) and both experimentally and in quantum MD simulations for the hydrated electron (Schwartz, B.J.; Rossky, P.J. Phys. Rev. Lett. 1994, 72, 3282. Reid, P.J.; Silva, C.; Walhout, P.K.; Barbara, P.F. Chem. Phys. Lett. 1994, 228, 658).
99. Polarized hole-burning provides the possibility of spectrally separating multiple electronic transitions with orthogonally oriented transition dipoles, as has been done experimentally for the permanganate anion (Yu, J.W.; Berg, M. J. Phys. Chem. 1993, 97, 1758) and both experimentally and in quantum MD simulations for the hydrated electron (Schwartz, B.J.; Rossky, P.J. Phys. Rev. Lett. 1994, 72, 3282. Reid, P.J.; Silva, C.; Walhout, P.K.; Barbara, P.F. Chem. Phys. Lett. 1994, 228, 658).
100. Polarized hole-burning provides the possibility of spectrally separating multiple electronic transitions with orthogonally oriented transition dipoles, as has been done experimentally for the permanganate anion (Yu, J.W.; Berg, M. J. Phys. Chem. 1993, 97, 1758) and both experimentally and in quantum MD simulations for the hydrated electron (Schwartz, B.J.; Rossky, P.J. Phys. Rev. Lett. 1994, 72, 3282. Reid, P.J.; Silva, C.; Walhout, P.K.; Barbara, P.F. Chem. Phys. Lett. 1994, 228, 658).
101. For the theoretical treatment of diffusive recombination of solvated electrons generated from multiphoton ionization or absorption of high energy radiation, see, e.g.: Green, N.J.B. Chem. Phys. Lett. 1984, 107, 485. Clifford, P.; Green, N.J.B.; Pilling, M.J. J. Phys. Chem. 1982, 86, 1318. Goulet, T.; Jay-Gerin, J.-P. J. Chem. Phys. 1992, 96, 5076. Green, N.J.B.; Pilling, M.J.; Pimblott, S.M.; Clifford, P. J. Phys. Chem. 1990, 94, 251.
102. For the theoretical treatment of diffusive recombination of solvated electrons generated from multiphoton ionization or absorption of high energy radiation, see, e.g.: Green, N.J.B. Chem. Phys. Lett. 1984, 107, 485. Clifford, P.; Green, N.J.B.; Pilling, M.J. J. Phys. Chem. 1982, 86, 1318. Goulet, T.; Jay-Gerin, J.-P. J. Chem. Phys. 1992, 96, 5076. Green, N.J.B.; Pilling, M.J.; Pimblott, S.M.; Clifford, P. J. Phys. Chem. 1990, 94, 251.
103. For the theoretical treatment of diffusive recombination of solvated electrons generated from multiphoton ionization or absorption of high energy radiation, see, e.g.: Green, N.J.B. Chem. Phys. Lett. 1984, 107, 485. Clifford, P.; Green, N.J.B.; Pilling, M.J. J. Phys. Chem. 1982, 86, 1318. Goulet, T.; Jay-Gerin, J.-P. J. Chem. Phys. 1992, 96, 5076. Green, N.J.B.; Pilling, M.J.; Pimblott, S.M.; Clifford, P. J. Phys. Chem. 1990, 94, 251.
104. For the theoretical treatment of diffusive recombination of solvated electrons generated from multiphoton ionization or absorption of high energy radiation, see, e.g.: Green, N.J.B. Chem. Phys. Lett. 1984, 107, 485. Clifford, P.; Green, N.J.B.; Pilling, M.J. J. Phys. Chem. 1982, 86, 1318. Goulet, T.; Jay-Gerin, J.-P. J. Chem. Phys. 1992, 96, 5076. Green, N.J.B.; Pilling, M.J.; Pimblott, S.M.; Clifford, P. J. Phys. Chem. 1990, 94, 251.
105. For recent experimental studies of solvated electrons produced via multiphoton ionization, see: Thomsen, C.L.; Madsen, D.; Keiding, S.R.; Thøgersen, J. J. Chem. Phys. 1999, 110, 3453, and references therein.
106. Crowell, R.A.; Barrels, D.M.; J. Phys. Chem. 1996, 100, 17940.
107. - excitation wavelength changes the relative fraction of each of these transitions that is excited, thus changing the relative fraction of electrons that localize nearby or far from their parent sodium atoms.
108. It is possible to estimate the height of this barrier using theory, as in the fourth article in ref 14. However, at this time, there is not sufficient experimental data on the nature of the solvated electron in THF and the associated wave functions of the electron and sodide to perform such calculations with any accuracy. Our hope is that our quantum molecular dynamics simulations of the sodide/THF system that are currently in progress will allow us to determine the height of the barrier for back electron transfer from the solvated electron to the sodium core.
109. It is possible to estimate the height of this barrier using theory, as in the fourth article in ref 14. However, at this time, there is not sufficient experimental data on the nature of the solvated electron in THF and the associated wave functions of the electron and sodide to perform such calculations with any accuracy. Our hope is that our quantum molecular dynamics simulations of the sodide/THF system that are currently in progress will allow us to determine the height of the barrier for back electron transfer from the solvated electron to the sodium core.
110. A detailed examination reveals that the electron appearance time is slightly slower for blue excitation than for red, despite the fact that blue excitation results in a greater average ejection distance. This may result from the fact that a more significant local rearrangement of the solvent is required to produce a solvent-separated contact pair than to produce an immediate contact pair. The extra time for this rearrangement is reflected in the delayed appearance of the electron's equilibrium absorption; cf. Figure 8. In the delayed ejection model, this could be accounted for by assuming (slightly) different detachment rate constants in eqs 5 and 6.
111. Dye, J.L.; Andrews, C.W.; Ceraso, J.M. J. Phys. Chem. 1975, 79, 3076. Ceraso, J.M.; Dye, J.L. J. Chem. Phys. 1974. 61, 1585. Dalton, L.R.; Rynbrandt, J.D.; Hansen, E.M.; Dye, J.L.; J. Chem. Phys. 1966, 44. 3969.
112. Dye, J.L.; Andrews, C.W.; Ceraso, J.M. J. Phys. Chem. 1975, 79, 3076. Ceraso, J.M.; Dye, J.L. J. Chem. Phys. 1974. 61, 1585. Dalton, L.R.; Rynbrandt, J.D.; Hansen, E.M.; Dye, J.L.; J. Chem. Phys. 1966, 44. 3969.
113. Dye, J.L.; Andrews, C.W.; Ceraso, J.M. J. Phys. Chem. 1975, 79, 3076. Ceraso, J.M.; Dye, J.L. J. Chem. Phys. 1974. 61, 1585. Dalton, L.R.; Rynbrandt, J.D.; Hansen, E.M.; Dye, J.L.; J. Chem. Phys. 1966, 44. 3969.
114. Similar translational motions into the angular node of a wave function have also been seen in simulation studies of the solvent relaxation following photoexcitation of the hydrated electron. See, e.g.: Schwartz, B. J.: Rossky, P.J. J. Chem. Phys. 1994, 101, 6902 ref 33.
115. Peon, J.; Hess, G.C.; Pecourt, J.-M.L.; Yuzawa, T.; Kohler, B.J. Phys. Chem. 1999, 103, 2460.
116. Barthel, E.R.; Martini, I.B.; Schwartz, B.J. Manuscript in preparation.
117. Martini, I.B.; Barthel, E.R.; Schwartz, B.J. Science 2001, 293, 492.
118. Kambhampati. P.; Son, D.H.; Kee. T.W.; Barbara, P.F. Chem. Phys. Lett. 2001, 342, 571.