Exposing solvent's roles in electron transfer reactions: Tunneling pathway and solvation

Journal of Physical Chemistry A

Volumn 107, Issue 19, 2003, Pages 3580-3597

  Zimmt, M B ^a   Waldeck, D H ^b  

^a BROWN UNIVERSITY   (United States)

^b UNIVERSITY OF PITTSBURGH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COMPOSITION EFFECTS; ELECTRON ENERGY LEVELS; ELECTRON MOBILITY; ELECTRON TUNNELING; FREE ENERGY; MATHEMATICAL MODELS; MOLECULES; REACTION KINETICS; SOLVENTS; THERMAL EFFECTS;

DONOR SPACER ACCEPTOR MOLECULES; ELECTRON MEDIATED SUPEREXCHANGE; ELECTRON TRANSFER REACTIONS; NONCOVALENT CONTACTS; SOLVATION; TUNNELING PATHWAY;

CHARGE TRANSFER;

EID: 0037672871     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp022213b     Document Type: Article

References (152)

1. (a) Closs, G. L.; Miller, J. R. Science 1988, 240 440.
2. (b) Paddon-Row, M. N. Acc. Chem. Res. 1994, 27, 18.
3. (c) Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13148.
4. (a) Oevering, H.; Paddon-Row, M. N.; Heppener, M.; Oliver, A. M.; Costaris, E.; Verhoeven, J. W.; Hush, N. S. J. Am. Chem. Soc. 1987, 109, 3258.
5. (b) Gloss, G. L.; Calcaterra, L. T.; Green, N. J.; Penfield, K. W.; Miller, J. R. J. Phys. Chem. 1986, 90, 3673.
6. (c) Helms, A.; Heiler, D.; McLendon, G. J. Am. Chem. Soc. 1992, 114, 6227.
7. (d) Leland, B. A.; Joran, A. D.; Felker, P. M.; Hopfield, J. J.; Zewail, A. H.; Dervan, P. B. J. Phys. Chem. 1985, 89, 5571.
8. (a) Helms, A.; Heiler, D.; McClendon, G. J. Am. Chem. Soc. 1991, 113, 4325.
9. (b) Sakata, Y.; Tsue, H.; O'Neil, M. P.; Wiederrecht, G. P.; Wasielewski, M. R. J. Am. Chem. Soc. 1994, 116 (6), 6904.
10. (c) Guldi, D. M.; Luo, C.; Prato, M.; Troisi, A.; Zerbetto, F.; Scheloske, M.; Dietel, E.; Bauer, W.; Hirsch, A. J. Am. Chem. Soc. 2001, 123, 9166.
11. (a) Penfield, K. W.; Miller, J. R.; Paddon-Row, M. N.; Cotsaris, E.; Oliver, A. M.; Hush, N. S. J. Am. Chem. Soc. 1987, 109, 5063.
12. (b) Stereochemical effects on electron transfer in complexes have been extensively investigated. Pispisa, B.; Venanzi, M.; Palleschi, A. J. Chem. Soc. Far. Trans. 1994, 90, 435.
13. (a) Finckh, P.; Heitele, H.; Volk, M.; Michel-Beyerle, M. E. J. Phys. Chem. 1988, 92, 6584.
14. (b) Wasielewski, M. R.; Niemczyk, M. P.; Johnson, D. G.; Svec, W. A.; Minsek, D. W. Tetrahedron 1989, 45, 4785.
15. (c) Zehnacker, A.; Lahmani, F.; Van Walree, C. A.; Jenneskens, L. W. J. Phys. Chem. A. 2000, 104, 1377.
16. (a) Zusman, L. D Z. Phys. Chem. 1994, 186, 1.
17. (b) Onuchic, J. N.; Beratan, D. N.; Hopfield, J. J. J. Phys Chem. 1986, 90, 3707.
18. (a) Jortner, J. J. Chem. Phys. 1976, 64, 4860.
19. (b) Bixon, M.; Jortner, J. Adv. Chem. Phys. 1999, 106, 35.
20. (a) Kelley, A. M. J. Phys. Chem. A 1999, 103, 6891.
21. (b) Spears, K. G.; Wen, X.; Zhang, R. J. Phys. Chem. 1996, 100, 10206.
22. (c) Wang, C.; Mohney, B. K.; Williams, R.; Hupp, J. T.; Walker, G. C. J. Am. Chem. Soc. 1998, 120, 5848.
23. (d) Markel, F.; Ferris, N. S.; Gould, I. R.; Myers, A. B. J. Am. Chem. Soc. 1992, 114, 6208.
24. (a) The charge-separated state has been observed via charge-transfer fluorescence from shorter spacer systems and by transient absorbance of the anthracene radical cation in 1.
25. (b) N. Segal. Undergraduate Thesis, Brown University, Providence, RI.
26. Corroborating evidence for equilibrium between the locally excited and charge transfer states of 1 in benzene was obtained from transient absorption spectroscopy. The formation and decay rate constants of the anthracene radical cation are the same as the two rate constants observed using time-resolved fluorescence spectroscopy.
27. Gu, Y.; Kumar, K.; Lin Z.; Read, I.; Zimmt, M. B.; Waldeck, D. H. J. Photochem. Photobiol. A. 1997, 105, 189.
28. Read, I.; Napper, A.; Kaplan, R.; Zimmt, M. B.; Waldeck, D. H. J. Am. Chem. Soc. 1999, 121, 10976.
29. 1.
30. (a) Marcus, R. A. J. Phys. Chem. 1989, 93, 3078.
31. (b) Cortes, J.; Heitele, H.; Jortner, J. J. Phys. Chem. 1994, 98, 2527.
32. (c) Matyushov, D. V.; Newton, M. D. J. Phys. Chem. A 2001, 105, 8516.
33. (d) Hush, N, S. Prog. Inorg. Chem. 1967, 8, 391.
34. (a) Zeng, Y.; Zimmt, M. B. J. Phys. Chem. 1992, 96, 8395.
35. (b) Zeng, Y.; Zimmt, M. B. J. Am. Chem. Soc. 1991, 113, 5107.
36. Kumar, K.; Kurnikov, I.; Beratan, D. N.; Waldeck, D. H.; Zimmt, M. B. J. Phys. Chem. A 1998, 102, 5529.
37. (a) Sitkoff, D.; Sharp, K. A.; Honig, B. J. Phys. Chem. 1994, 98, 1978.
38. (b) Sharp, K.; Honig, B. Annu. Rev. Biophys. Biophys. Chem. 1990, 19, 301.
39. (c) Newton, M. D.; Basilevsky, M. V.; Rostov, I. V. Chem. Phys. 1998, 232, 201.
40. (a) Jeon, J.; Kim, H. J. J. Phys. Chem. A 2000, 104, 9812.
41. (b) Dorairaj, S.; Kim, H. J. J. Phys. Chem. A 2002, 106, 2322.
42. Matyushov, D. V.; Voth, G. A. J. Chem. Phys. 1999, 111, 3630.
43. Read, I.; Napper, A.; Zimmt, M. B.; Waldeck, D. H. J. Phys. Chem. A 2000, 104, 9385.
44. Napper, A. M.; Read, I.; Kaplan, R.; Zimmt, M. B.; Waldeck, D. H. J. Phys. Chem. A 2002, 106, 5288.
45. Napper, A. M.; Read, I.; Waldeck, D. H.; Kaplan, R. W.; Zimmt, M. B.; J. Phys. Chem. A 2002, 106, 4784.
46. Brunschwig, B. S.; Ehrenson, S.; Sutin, N. J. Phys. Chem. 1986, 90, 3657.
47. (a) Peng, B.-C.; Newton, M. D.; Raineri, F. O.; Friedman, H. L. J. Chem. Phys. 1996, 104, 7153.
48. (b) Peng, B.-C.; Newton, M. D.; Raineri, F. O.; Friedman, H. L. J. Chem. Phys. 1996, 104, 7177.
49. Although initial results are encouraging, whether the inclusion of quadrupolar responses is successful at extending continuum treatments to nonpolar and weakly polar solvents remains an open question.
50. (a) Vath, P.; Zimmt, M. B.; Matyushov, D. V.; Voth, G. A. J. Phys. Chem. B 1999, 103, 9130.
51. (b) Vath, P.; Zimmt, M. B. J. Phys. Chem. A 2000, 104, 2626.
52. Gray, C. G.; Gubbins, K. E. Theory of Molecular Fluids, Vol. 1; Clarendon Press: Oxford, 1984.
53. (a) Matyushov, D. V.; Schmid, R. J. Chem. Phys. 1996, 104, 8627.
54. (b) Ben-Amotz, D.; Herschbach, D. R. J. Phys. Chem. 1990, 94, 1038.
55. Kumar, K. PhD Thesis, Brown University, Providence, RI, 1996.
56. This difference on polarizabilities is given more explicitly in refs 20 and 21.
57. The molecular solvation model assumes that the quadrapole is axial with its major axis along the dipole moment direction. Table S1 in the Supporting Information shows that the quadrupole moments in 2.5-dichlorotoluene and many of the alkylbenzenes are nonaxial; that is, the major axis of the quadrupole moment's principal axis system is not oriented along the dipole moment vectors direction and the other components of the quadrupole moment tensor are not equal in magnitude.
58. Gubbins, K. E.; Gray, C. G.; Machado, J. R. S. Mol. Phys. 1981, 42, 817.
59. nonaxial> with b an adjustable parameter.
60. vacG = 0.295 eV, and a radius = 7.8 Å.
61. A detailed presentation of the predicted reorganization energies for 1 in each of the solvents as a function of temperature is provided in the Supporting Information.
62. (a) Eigler, D. M.; Lutz, C. P.; Rudge, W. E. Nature (London) 1991, 352, 600.
63. (a) Segal, D.; Nitzan, A.; Ratner, M.; Davis, W. B. J. Phys. Chem. B 2000, 104, 2790.
64. (b) Sumi, H.; Kakitani, T. J. Phys. Chem. B. 2001, 105, 9603.
65. (c) Felts, A. K.; Pollard, W. T.; Friesner, R. A. J. Phys. Chem. 1995, 99, 2929.
66. Halpern, J.; Orgel, L. E. Discuss. Faraday. Soc. 1960, 29, 32.
67. McConnell, H. M. J. Chem. Phys. 1961, 35, 508.
68. (a) Evenson, J. W.; Karplus, M. D. Science 1993, 262, 1247.
69. (b) Paddon-Row, M. N.; Shephard, M. J.; Jordan, K. D. J. Am. Chem. Soc. 1993, 115, 3312.
70. (c) Larsson, S. J. Am. Chem. Soc. 1981, 103, 4034.
71. (a) Newton, M. D. Chem. Rev. 1991, 91, 767.
72. b) Jordan, K. D.; Paddon-Row, M. N. Chem. Rev. 1992, 92, 295.
73. (a) Liang, C.; Newton, M. D. J. Phys. Chem. 1993, 97, 3199.
74. (b) Jortner, J.; Bixon, M.; Voityuk, A. A.; Roesch, N. J. Phys. Chem. A 2002, 106, 7599.
75. (c) Sikes, H. D.; Smalley, J. F.; Dudek, S. P.; Cook, A. R.; Newton, M. D.; Chidsey, C. E. D.; Feldberg, S. W. Science 2001, 291, 1519.
76. (d) Winkler, J. R.; Gray, H. B. J. Biol. Inorg. Chem. 1997, 2, 399.
77. Beratan, D. N.; Onuchic, J. N. Photosyn. Res. 1989, 22, 173.
78. (a) Balabin, I. A.; Onuchic, J. N. J. Phys. Chem. 1996, 100, 11573.
79. (b) Naleway, C. A.; Curtiss, L. A.; Miller, J. R. J. Phys. Chem. 1991, 95, 8434.
80. (c) Ratner, M. D. J. Phys. Chem. 1990, 94, 4877.
81. (a) Miller, J. R.; Beitz, J. V.; Huddleston, R. K. J. Am. Chem. Soc. 1984, 106, 5057.
82. (b) Launay, J.-P. Chem. Soc. Rev. 2001, 30, 386.
83. (c) Fernando, S. R. L.; Kozlov, G. V.; Ogawa, M. Y. Inorg. Chem. 1998, 37, 1900.
84. (d) See also refs 1 and 2.
85. Recent experimental and theoretical studies indicate alternatives to superexchange type mechanisms for long distance electron transfer. The fall off of transfer rates with distance by these mechanisms is much weaker than for superexchange mechanisms. See refs 37 and 41.
86. Tong, G. S. M.; Kurnikov, I. V.; Beratan D. N. J. Phys. Chem. B, 2002, 106, 2381.
87. Benrahmoune, M.; Filali-Mouhim, A.; Jay-Gerin, J.-P. Can. J. Phys. Pharm. 2001, 79, 122.
88. Beratan, D. N.; Hopfield, J. J. J. Am. Chem. Soc. 1984 106, 1584.
89. Beratan, D. N. J. Am. Chem. Soc. 1986, 108, 4321.
90. Reed, A. E.; Curtis, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.
91. Petrov, E. G.; Zelinsky, Y. R.; May, V. J. Phys. Chem. 2002, 106, 3092.
92. (a) Davis, W. B.; Ratner, M. A.; Wasielewski, M. R. Chem. Phys. 2002, 281, 333.
93. (b) Giese B Annu. Rev. Biochem. 2002, 71, 51.
94. (a) Osuka, A.; Maruyama, K.; Mataga, N.; Asahi, T.; Yamazaki, I.; Tamai, N. J. Am. Chem. Soc. 1990, 112, 4958.
95. (b) McLendon, G.; Helms, A.; Heiler, D. J. Am. Chem. Soc. 1992, 114, 6227.
96. (c) Kang, Y. K.; Rubtsov, I. V.; Iovine, P. M.; Chen, J.; Therien, M. J. J. Am. Chem. Soc. 2002, 124, ASAP.
97. Miller, S. E.; Marsh, E. M.; Svec, W. A.; Debreczeny, M. P.; Wasielewski, M. R. Book of Abstracts, 216th ACS National Meeting, Boston, 1998, PHYS-132.
98. Tsue, H.; Imahori, H.; Kaneda, T.; Tanaka, Y.; Okada, T.; Tamaki, K.; Sakata, Y. J. Am. Chem. Soc. 2000, 122, 2279.
99. Miller, J. R. New J. Chem. 1987, 11, 83.
100. (a) Balabin, I. A.; Onuchic, J. N. Science 2000, 290, 114.
101. (b) Xie, Q.; Archontis, G.; Skourtis, S. S. Chem. Phys. Lett. 1999, 312, 237.
102. (c) Medvedev, E. S.; Stuchebrukhov, A. A. J. Chem. Phys. 1997, 107, 3821.
103. (d) Tang, J. J. Chem. Phys. 1993, 98, 6263.
104. (e) Hoffman, B. M.; Ratner, M. A.; Wallin, S. A. Adv. Chem. Ser. 1990, 226, 125.
105. (f) Xu, Q.; Baciou, L.; Sebban, P.; Gunner, M. R. Biochemistry 2002, 41, 10021.
106. (a) Carapelluci, P. A.; Mauzerall, D. Ann. NY. Acad. Sci. B 1975, 244, 214.
107. (b) Ballard, S. G.; Mauzerall, D. Tunneling Biol. Syst. [Proc. Symp.] 1979, 581; Chance, B., Marcus, R. A., DeVault, D.C., Eds.
108. Oliver, A. M.; Craig, D. C.; Paddon-Row, M. N.; Kroon, J.; Verhoeven, J. W. Chem. Phys. Lett. 1988, 150, 366.
109. Liu, J.-Y.; Schmidt, J. A.; Bolton, J. R. J. Phys. Chem. 1991, 95, 6924.
110. (a) Ojima, S.; Miyasaka, H.; Mataga, N. J. Phys. Chem. 1990, 94, 7534.
111. (b) Yabe, T.; Kochi, J. K. J. Am. Chem. Soc. 1992, 114, 4491.
112. (a) Lawson, J. M.; Paddon-Row, M. N.; Schuddeboom, W.; Warman. J. M.; Clayton, A. H. A.; Ghiggino, K. P. J. Phys. Chem. 1993, 97, 13099.
113. (b) Seischab, M.; Lodenkemper, T.; Stockmann, A.; Schneider, S.; Koeberg, M.; Roest, M. R.; Verhoeven, J. W.; Lawson, J. M.; PaddonRow, M. N. Phys. Chem. Chem. Phys. 2000, 2, 1889.
114. Gould, I. R.; Mueller, L. J.; Farid, S. Zeit. Phys. Chem. N. F. 1991, 170, 143.
115. (a) Head, N. J.; Oliver, A. M.; Look, K.; Lokan, N. R.; Jones, G. A.; Paddon-Row, M. N. Angew Chem. Int. Ed. 1999, 38, 3219.
116. (b) Prigge, S. T.; Kolhekar, A. S.; Eipper, B. A.; Mains, R. E.; Amzel, L. M. Nature. Struct. Biol. 1999, 6, 976.
117. β in a vacuum is ∼2.7 Å. See: Henderson, T. M.; Cave, R. J. J. Chem. Phys. 1998, 109, 7414.
118. Lokan, N. R.; Paddon-Row, M. N.; Koeberg, M.; Verhoeven, J. W. J. Am. Chem. Soc. 2000, 122, 5075.
119. (a) Verhoeven, J. W. Adv. Chem. Phys. 1999, 106, 603.
120. (b) Cave, R. J.; Newton, M. D.; Kumar, K.; Zimmt, M. B. J. Phys. Chem. 1995, 99, 17501.
121. (a) Cave, R. J.; Newton, M. D. Chem Phys Lett 1996, 249, 15.
122. (b) Cave, R. J.; Newton, M. D. J. Chem. Phys. 1997, 106, 9213.
123. (a) There are systems where through bond coupling may exhibit significant fluctuations because of small structural changes. This includes electron-transfer systems involving conformational gating, structural fluctuations of proteins and symmetry breaking.
124. (b) Jones G. A.; Paddon-Row, M. N.; Carpenter, B. K.; Piotrowiak, P. J. Phys. Chem. A. 2002, 106, 5011.
125. (c) Reimers, J. R.; Hush, N. S. Chem. Phys. 1990, 146, 105.
126. S1).
127. (b) Milischuk, A.; Matyushov, D. V. submitted.
128. The Coulomb term will vary if the separations of D+ and S- change drastically with solvent. The fourth term varies insignificantly with solvent dielectric properties.
129. These calculations used a nonsymmetric conformation of the spacer and acceptor ester groups to avoid rigorous (mathematical) symmetry constraints on the coupling.
130. V = -0.9093E(6-31G**) + 2.507, with all values in eV.
131. Kaplan, R.; Napper, A. M.; Waldeck, D. H.; Zimmt, M. B. J. Phys. Chem. A. 2002, 106, 1917.
132. The 40-fold drop is premised on a through space decrease of wave function overlap and exchange arising from a β value of -2.6/Å.
133. 1/2 from 1 to 3 may reflect, in part, the change from symmetry forbidden donor-acceptor topology in 1 to a symmetry allowed donor-acceptor topology in 3. As most in-cleft solvent configurations for both molecules are dissymmetric, the symmetry forbidden nature of the donor-acceptor interaction for 1 should not be heavily expressed in the donor-spacer and spacer-acceptor interactions.
134. β for the 7.5 and 9.5 Å U-shaped molecules was estimated using rate constants extracted from Figure 3B in ref 66. To one significant figure, the β values are 1 (in TIP, benzene, o-dichlorobenzen, acetonitrile), 0.8 (ethyl acetate), 0.4 (benzylcyanide, tetrahydrofuran), and 0.3(dibutyl ether, diethyl ether).
135. 2 group eliminates a set of solvent configurations that otherwise might estabilish significant exchange interactions with both the donor and the acceptor. For the purposes of investigating the distance dependence of solvent-mediated coupling, this spacer is inadequate.
136. A molecular mechanics calculation was performed on each of the 78 configurations of benzene within the cleft of 1. These energies were used to calculate the relative probability of each configuration.
137. This results from the symmetry forbidden topology that causes the average electronic coupling to be near zero. For a system in which the direct interaction was symmetry allowed, the average value would be more comparable to the root-mean-square value.
138. The rate constants for 1 in mesitylene exhibit similar variations with temperatures but have been measured over a smaller temperature range.
139. rG decreases from +0.04 eV to 0.0 eV.
140. rG > 0 eV), the calculated FCWDS are too large. This implies that the actual decrease in |V| at temperatures above 315 K will be steeper than indicated in the present analysis.
141. Formation of a DSA-solvent "complex" is likely attended by a decrease in entropy. For aromatic solvents with small or no alkyl groups, ΔH for formation of this complex may be negative or close to zero. For aromatic solvents with bulky alkyl groups. ΔH for complex formation will be more positive.
142. (a) Castner, E. W.; Kennedy, D.; Cave, R. J. J. Phys. Chem. A 2000, 104, 2869.
143. (b) Troisi, A.; Ratner, M., manuscript in preparation.
144. Nelsen, S. F.; Ismagilov, R. F.; Gentile, K. E.; Powell, D. R. J. Am. Chem. Soc. 1999, 121, 7108.
145. (a) Khoshtariya, D. E.; Dolidze, T. D.; Zusman, L. D.; Waldeck, D. H. J. Phys. Chem. A. 2001, 105, 1818.
146. (b) Weaver, M. J. Chem. Rev. 1992, 92, 463.
147. (a) Diner, B. A.; Rappaport, F. Annu. Rev. Plant Biol. 2002, 53, 551.
148. (b) Hoff, A. J.; Deisenhofer, J. Phys. Rep. 1997, 287, 1.
149. (c) Ivashin, N.; Larsson, S. J. Phys. Chem. B 2002, 106, 3996.
150. (a) Napper, A. M.; Head, N. J.; Oliver, A. M.; Shephard, M. J.; Paddon-Row, M. N.; Read, I.; Waldeck, D. H. J. Am. Chem. Soc. 2002, 124, 10171.
151. (b) Napper, A. M.; Read, I.; Waldeck, D. H.; Head, N. J.; Oliver, A. M.; Paddon-Row, M. N. J. Am. Chem. Soc. 2000, 122, 5220.
152. Fidler, V.; Kapusta, P., personal communication.