Nonlinear free energy relations for adiabatic proton transfer reactions in a polar environment. II. Inclusion of the hydrogen bond vibration

Journal of Physical Chemistry A

Volumn 106, Issue 9, 2002, Pages 1850-1861

  Kiefer, Philip M ^a   Hynes, James T ^a,b  

^a UNIVERSITY OF COLORADO   (United States)

^b ECOLE NORMALE SUPÉRIEURE   (France)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVATION ENERGY; ELECTRON TRANSITIONS; ELECTRONIC STRUCTURE; FREE ENERGY; HYDROGEN BONDS; PROTONS; QUANTUM THEORY;

ACTIVATION FREE ENERGY;

CHARGE TRANSFER;

EID: 0037035158     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp013425w     Document Type: Article

References (90)

1. (a) Bell, R.P. The Proton in Chemistry, 2nd ed.; Cornell University Press: Ithaca, NY, 1973.
2. (b) Caldin, E.; Gold, V. Proton-Transfer Reactions; Chapman and Hall: London, 1975.
3. (c) Kresge, A.J. Acc. Chem. Res. 1975, 8, 354.
4. (d) Kresge, A.J. In Isotope Effects on Enzyme-Catalyzed Reactions; Cleland, W.W., O'Leary, M.H., Northrop, D.B., Eds.; University Park Press: Baltimore, MD, 1977; p 37.
5. (a) Marcus, R.A. Faraday Symp. Chem. Soc. 1975, 10, 60.
6. (b) Marcus, R.A. J. Phys. Chem. 1968, 72, 891.
7. Cohen, A.O.; Marcus, R.A. J. Phys. Chem. 1968, 72, 4249.
8. (d) Marcus, R.A. J Am. Chem. Soc. 1969, 91, 7224.
9. (a) Kreevoy, M.M.; Konasewich, D.E. Adv. Chem. Phys. 1972, 21, 243.
10. (b) Kreevoy, M.M.; Oh, S.-w. J. Am. Chem. Soc. 1973, 95, 4805.
11. Warshel, A. Computer Modeling of Chemical Reactions in Enzymes and Solutions; John Wiley and Sons: New York, 1991.
12. Pines, E.; Magnes, B.-Z.; Lang, M.J.; Fleming, G.R. Chem. Phys. Lett 1997, 281, 413.
13. (a) Kresge, A.J.; Silverman, D.N. Methods Enzymol. 1999, 308, 276.
14. (b) Gerlt, J.A.; Gassman, P.G. J. Am. Chem. Soc. 1993, 115, 11 552.
15. (a) Kong, Y.S.; Warshel, A.; J. Am. Chem. Soc. 1995, 117, 6234.
16. (b) Warshel, A.; Schweins, T.; and Fothergil, M. J. Am. Chem. Soc. 1994, 116, 8437.
17. (c) Schweins, T.; Warshel, A.; Biochemistry 1996, 35, 14 232.
18. Kiefer, P.M.; Hynes, J.T. J. Phys. Chem. A 2002, 106, 1834.
19. Melander, L; Saunders: W.H. Reaction Rates of Isotopic Molecules; John Wiley and Sons: New York, 1980.
20. (a) Mulliken, R.S. J. Phys. Chem. 1952, 56, 801.
21. (b) Mulliken, R.S.; Person, W.B. Molecular Complexes; John Wiley and Sons: New York, 1969.
22. (c) Mulliken, R.S. J. Chim. Phys. 1964, 20, 20.
23. Timoneda, J.J.; Hynes, J.T. J. Phys. Chem. 1991, 95, 10 431.
24. (b) Ando, K.; Hynes, J.T. J. Phys. Chem. A 1999 103, 10 398.
25. (b) Ando, K.; Hynes, J.T. J. Phys. Chem. B 1997, 101, 10 464.
26. Staib, A.; Borgis, D.; Hynes, J.T. J. Chem. Phys. 1995, 102, 2487.
27. The treatment of ref 13 utilizes a curve-crossing formalism, in which the solvent - H-bond coordinate coupling arises from the mixing of the proton nuclear diabatic states, as opposed to the electronic mixing described here and in I. The curve-crossing picture can be recovered from the present picture by extracting the proton coupling from the proton potentials. The link between the two is provided by the fact that the electronic coupling determines the proton potentials which in turn determine the proton coupling.
28. (a) Basilevsky, M.V.; Soudackov, A.; Vener, M.V. Chem. Phys. 1995, 200, 87.
29. (b) Basilevsky, M.V.; Verier, M.V.; Davidovich, G.V.; Soudackov, A. Chem. Phys. 1996, 208 267.
30. (c) Vener, M.V.; Rostov, I.V.; Soudackov, A.; Basilevsky, M.V.; Chem. Phys. 2000, 254, 249.
31. (a) Steinet, T.; Saenger, W. Acta Crystallog. Sec. B 1994, 348.
32. (b) Steinet, T. J. Chem. Soc., Chem. Commun. 1995, 1331.
33. (a) Smirnov, S.N.; Benedict, H.; Golubev, N.S.; Denisov, G.S.; Kreevoy, M.M.; Schowen, R.L.; Limbach, H.-H. Can. J. Chem. 1999, 77, 943.
34. (b) Benedict, H.; Limbach, H.-H.; Wehlan, M.; Fehlhammer, W.-P.; Golubev, N.S.; Janoscheck, R. J. Am. Chem. Soc. 1998, 120, 2939.
35. (a) Borgis, D.; Hynes, J.T. J. Phys. Chem. 1996, 100, 1118.
36. (b)Borgis, D.; Hynes, J.T. Chem. Phys. 1993, 170, 315.
37. (c) Borgis, D.; Lee, S.; Hynes, J.T. Chem. Phys. Lett. 1989, 162, 19.
38. (d) Lee, S.; Hynes, J.T. J. Chim. Phys. 1996, 93, 1783.
39. (a) Aqvist, J.; Warshel, A. Chem. Rev. 1993, 93, 2523.
40. (b) Hwang, J.-K.; King, G.; Creighton, S.; Warshel, A. J. Am. Chem. Soc. 1988, 110, 5297.
41. (c) Warshel, A.; Hwang, J.-K.; Faraday Discuss. 1992, 93, 225.
42. (a) Dogonadze, R.R.; Kuznetzov, A.M.; Levich, V.G. Electrochim. Acta 1968, 13, 1025.
43. (b) German, E.D.; Kuznetzov, A.M.; Dogonadze, R.R. J. Chem. Soc., Faraday Trans. 2 1980, 76, 1128.
44. (c) Ulstrup, J. Charge-Transfer Processes in Condensed Media; Springer: Berlin, 1979.
45. (d) Kuznetzov, A.M. Charge Transfer in Physics, Chemistry and Biology: Physical Mechanisms of Elementary Processes and an Introduction to the Theory; Gordon and Breach Pubs.: Amsterdam, 1995.
46. (e) Kuznetzov, A.M. and Ulstrup, J. Can. J. Chem. 1999, 77, 1085.
47. (f) Sühnel, J.; Gustav, K. Chem. Phys. 1984, 87, 179.
48. Pimentel, G.C.; McClellan, A.L. The Hydrogen Bond; W.H. Freeman: New York, 1960.
49. This feature is absent in the model calculations of ref 13, in which the basic model Hamiltonian is not constructed quantum mechanically, and the electronic coupling does not enter explicitly, and thus effects due to its variation are absent.
50. 13,14.
51. -1). Indeed, one might wish to quantize a portion of these librations in a more sophisticated treatment. However, this would require the introduction of more than one solvent coordinate in the analysis, and it is likely to be only worth doing in connection with a detailed realistic computer simulation.
52. Pauling, L. J. Am. Chem. Soc. 1947, 69, 542.
53. 27 where the quantum particle tunnels through the barrier in its coordinate.
54. (a) Babamov, V.K.; Marcus, R.A. J. Chem. Phys. 1981, 74, 1790.
55. (b) Hiller, C.; Manz, J.; Miller, W.H.; Römelt, J. J. Chem. Phys. 1983, 74, 3850.
56. (c) Miller, W.H. J. Am. Chem. Soc. 1979, 101, 6819.
57. (d) Skodje, R.T.; Truhlar, D.G.; Garrett, B.C. J. Chem. Phys. 1982, 77, 5955.
58. (e) Marcus, R.A.; Coltrin, M.E. J. Chem. Phys. 1977, 67, 2609.
59. (f) Garrett, B.C.; Truhlar, D.G. J. Chem. Phys. 1983, 79, 4931.
60. (g) Kim, Y.; Kreevoy, M.M. J. Am. Chem. Soc. 1992, 114, 7116.
61. o(Q;δE)>, where the ground-state wave functions for Q and q are taken from eq 2.5 and eq 2.13 in I, respectively.
62. (a) Hammond, G.S. J. Am. Chem. Soc. 1955, 77, 334.
63. (b) Lowry, T.H.; Richardson, K.S. Mechanism and Theory in Organic Chemistry, 3rd ed.; Harper Collins Publishers: New York, 1987.
64. (a) Marcus, R.A. J. Chem. Phys. 1956, 24, 979.
65. (b) Marcus, R.A. J. Chem. Phys. 1956, 24, 966.
66. (c) Marcus, R.A.; Sutin, N. Biochim. Biophys. Acta 1985, 811, 265.
67. (d) Sutin, N. Prog. Inorg. Chem. 1983, 30, 441.
68. RXN = 0 for the intrinsically asymmetric case, but the deviation from 1/2 is small.
69. A corresponding analysis of the complete thermally activated rate constant could be done with separate but identical decompositions for higher H-bond vibrational states (e.g. i = 1), where these relationships would be included with the ground-state case i = 0 in eqs 2.7 and 2.8.
70. (a) Agmon, N.; Levine, R.D. Chem. Phys. Lett. 1977, 52, 197.
71. (b) Agmon, N.; Levine, R.D. J. Chem. Phys. 1979, 71, 3034.
72. (c) Agmon, N.; Levine, R.D. Israel J. Chem. 1980, 19, 330.
73. Kiefer, P.M.; Hynes, J.T., in preparation.
74. Sutin, N. Prog. Inorg. Chem. 1983, 30, 441.
75. 31 However, eq 3.13 does not preclude exchange reactions and hence does not predict a proper Brønsted coefficient.
76. (a) Hwang, J.-K.; Warshel, A. J. Phys. Chem. 1993, 97, 10 053.
77. (b) Hwang, J.-K.; Chu, Z.T.; Yadav, A.; Warshel, A. J. Phys. Chem. 1991, 95, 8445.
78. (c) Hwang, J.-K.; Warshel, A. J. Am. Chem. Soc. 1996, 118, 11 745.
79. 37 will thus only be correct for a symmetric reaction.
80. 34.
81. 18,20.
82. In contrast to eq 3.13, the analysis in ref 18a gives a proper Bronsted coefficient for a symmetric reaction case, although the analysis is restricted to large solvent reorganization energy.
83. (a) Agmon, N. J. Am. Chem. Soc. 1980, 102, 2164.
84. (b) Marcus, R.A. J. Am. Chem. Soc. 1969, 91, 7224.
85. (c) Bernasconi, C.F. J. Am. Chem. Soc. 1997, 119, 4008.
86. (d) Bernasconi, C.F. Acc. Chem. Res. 1987, 20, 301.
87. (e) Bordwell, F.G.; Boyle, W.J., Jr. J. Am. Chem. Soc. 1974, 94, 3907.
88. (f) Pross, A. Adv. Phys. Org. Chem. 1985, 21, 99.
89. (g) Pross, A.; Shaik, S. J. Am. Chem. Soc. 1982, 104, 1129.
90. Baksic, D.; Bertran, J.; Lluch, J.M.; Hynes, J.T. J. Phys. Chem. A 1998, 102, 3977.