Molecular mechanism of HF acid ionization in water: An electronic structure-Monte Carlo study

Journal of Physical Chemistry A

Volumn 103, Issue 49, 1999, Pages 10398-10408

  Ando, Koji ^a   Hynes, James T ^b  

^a UNIVERSITY OF TSUKUBA   (Japan)

^b UNIVERSITY OF COLORADO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000991264     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp992481i     Document Type: Article

References (131)

1. Bell, R. P. The Proton in Chemistry; Chapman and Hall: London, 1973.
2. Caldin, E. F., Gold, V., Eds. Proton Transfer Reactions; Chapman and Hall: London, 1975.
3. Bell, R. P. The Tunnel Effect in Chemistry; Chapman and Hall: London, 1980.
4. Buncel, E., Lee, C. C., Eds. Isotope Effects in Organic Chemistry; Elsevier: Amsterdam, Vol. 2, 1976;
5. Hibbert, F. Adv. Phys. Org. Chem. 1986, 22, 113.
6. Hibbert, F. Adv. Phys. Org. Chem. 1990, 26, 255.
7. Westheimer, F. H. Chem. Rev. 1961, 61, 265.
8. (a) Kosower, E. M.; Huppert, D. Annu. Rev. Phys. Chem. 1986, 37, 127.
9. Kreevoy, M. M.; Truhlar, D. G. In Rates and Mechanisms of Reactions, 4th ed.; Bemasconi, C. F., Ed.; Wiley: New York, 1986, Chapter 1.
10. Ratajczak, H. In Electron and Proton Transfer Processes in Chemistry and Biology; Müller, A., Ratajczak, H., Junge, W., Diemann, E., Eds.; Elsevier: Amsterdam, 1992.
11. (b) Bountis, T., Ed. Proton Transfer in Hydrogen-Bonded Systems; Plenum: New York, 1993.
12. (c) See also the special issues on proton transfer: Chem. Phys. 1989, 136, 2,
13. J. Phys. Chem. 1991, 95, 25,
14. and Ber. Bunsenges. Phys. Chem. 1998, 102, 3.
15. Jencks, W. P. Catalysis in Chemistry and Enzymology; McGraw-Hill: New York, 1969.
16. Bender, M. L. Mechanisms of Homogeneous Catalysis from Protons to Proteins; Wiley: New York, 1971.
17. Fersht, A. Enzyme Structure and Mechanism; W. H. Freeman: New York, 1985;
18. Gandour, R. D.; Schowen, R. L. Transition States of Biochemical Processes; Plenum: New York, 1978.
19. Klinman, J. P. CRC Crit. Rev. Biochem. 1981, 10, 39.
20. Menger, F. Acc. Chem. Res. 1993, 26, 206.
21. Gutman, M.; Nachliel, E. Biochim. Biophys. Acta. 1990, 391, 1015.
22. Eigen, M.; Kruse, W.; De Maeyer, L. Prog. React. Kinet. 1964, 2, 285.
23. Eigen, M. Angew. Chem., Int. Ed. Engl. 1964, 3, 1;
24. Pure Appl. Chem. 1963, 6, 97.
25. Albery, W. J. Prog. React. Kinet. 1967, 4, 353. Maxrchal, Y. In ref 2b.
26. Borgis, D.; Lee, S.; Hynes, J. T. Chem. Phys. Lett. 1989, 762, 19.
27. Borgis, D.; Hynes, J. T. J. Chem. Phys. 1991, 94, 3619;
28. Chem. Phys. 1993, 770, 315.
29. Borgis, D.; Hynes, J. T. J. Phys. Chem. 1996, 700, 1118.
30. Juanós I; Timoneda, J.; Hynes, J. T. J. Phys. Chem. 1991, 95, 10431.
31. Staib, A.; Borgis, D.; Hynes, J. T. J. Chem. Phys. 1995, 102, 2487.
32. Ando, K.; Hynes, J. T. In Cramer, G. J.; Truhlar, D. G., Eds.; Structure and Reactivity in Aqueous Solution: Characterization of Chemical and Biological Systems; ACS Books: Washington DC, 1994.
33. J. Mol. Liq. 1995, 64, 25.
34. Ando, K.; Hynes, J. T. J. Phys. Chem. B 1997, 101, 10464.
35. Ando, K.; Hynes, J. T. Faraday Discuss. 1995, 102, 435.
36. Ando, K.; Hynes, J. T. Adv. Chem. Phys. 1999, 110, 381.
37. Azzouz, H.; Borgis, D. J. Chem. Phys. 1993, 98, 7361;
38. J. Mol. Liq. 1994, 61, 17.
39. Borgis, D.; Tarjus, G.; Azzouz, H. J. Phys. Chem. 1992, 96, 3188;
40. J. Chem. Phys. 1992, 97, 1390.
41. Warshel, A.; Weiss, R. M. J. Phys. Chem. 1980, 102, 6218.
42. Warshel, A.; Russel, S. J. Am. Chem. Soc. 1986, 108, 6569.
43. Warshel, A. Computer Modeling of Chemical Reactions in Enzymes and Solutions; Wiley: New York, 1991.
44. Laasonen, K.; Klein, M. L. J. Am. Chem. Soc. 1994, 116, 11620.
45. Giguere, P. A. J. Chem. Ed. 1979, 56, 571;
46. Chem. Phys. 1981, 60, 421.
47. Laasonen, K.; Klein, M. L. Mol. Phys. 1996, 88, 135.
48. Balbuena, P. B.; Johnston, K. P.; Rossky, P. J. J. Phys. Chem. 1996, 100, 2716.
49. Kapral, R.; Consta, S. J. Chem. Phys. 1994, 101, 10908;
50. 1996, 104, 4581.
51. Laria, D.; Kapral, R.; Estrin, D.; Ciccotti, G. J. Chem. Phys. 1996, 104, 6560.
52. Chipot, C.; Gorb, L. G.; Rivail, J.-L. J. Phys. Chem. 1994, 98, 1601.
53. Rivail, J.-L.; Antonczak, S.; Chipot, C.; Ruiz-López, M. F.; Gorb, L. G. In Structure, Energetics, and Reactivity in Aqueous Solution; Cramer, C. J., Truhlar, D. G., Eds.; ACS Books: Washington, DC, 1994.
54. Even if restricted to the theoretical arena, the general field of proton transfer research is now quite extensive. Some general sources of references here include refs 2 and 13, and the forthcoming special issues of Isr. J. Chem., edited by N. Agmon and M. Gutman.
55. Gertner, B. J.; Hynes, J. T. Science 1996, 271, 1563.
56. Gertner, B. J.; Hynes, J. T. Faraday Discuss. 1998, 110, 301.
57. Bianco, R.; Gertner, B. J.; Hynes, J. T. Ber. Bunsenges. Phys. Chem. 1998, 102, 518.
58. See also: Estrin, D. A.; Kohanoff, J.; Laria, D. H.; Weht, R. O. Chem. Phys. Lett. 1997, 280, 280.
59. Pauling, L. The Nature of the Chemical Bond; Cornell: Ithaca, NY, 1960.
60. Coulson, C. A. Valence; Oxford: London, 1961.
61. Mulliken, R. S. J. Phys. Chem. 1952, 56, 801 ;
62. J. Chim. Phys. 1964, 20, 20.
63. Coulson, C. A. In Hydrogen Bonding; Hadži, D., Thompson, H. W., Eds.; Pergamon: London, 1959.
64. Szczepaniak, K.; Tramer, A. J. Phys. Chem. 1967, 71, 3035.
65. Puranik, P. G.; Kumar, V. Proc. Indian Acad. Sci. 1963, 29, 58, 327.
66. Zwilles, B. A.; Parson, W. B. J. Chem. Phys. 1983, 79, 65.
67. Bacskay, G. B.; Hush, N. S. Chem. Phys. 1983, 82, 303.
68. Reed, A. E.; Curtis, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899. See also refs 8 and 11.
69. See the discussion remarks following ref 12.
70. Marcus, R. A. Annu. Rev. Phys. Chem. 1964, 15, 155.
71. Ulstrup, J. Charge Transfer Processes in Condensed Media; Springer-Verlag: Berlin, 1979.
72. Newton, M. D.; Sutin, N. Ibid. 1984, 35, 437.
73. Bagchi, B. Annu. Rev. Phys. Chem. 1989, 40, 115.
74. Barbara, P. F.; Meyer, T. J.; Ratner, M. A. J. Phys. Chem. 1996, 100, 13148.
75. An entree into the extensive literature may be found in: Marx, D.; Tuckerman, M. E.; Hutter, J.; Parrinello, M. Nature 1999, 397, 601.
76. Hynes, J. T. Nature 1999, 397, 565. See also refs 53 and 54 below.
77. See e.g.: Kierstead, W. P.; Wilson, K. R.; Hynes, J. T. J. Chem. Phys. 1991, 95, 5256, and references therein.
78. Dupuis, M.; Watts, J. D.; Villar, H. O.; Hurst, G. J. B. HONDO Ver. 7.0, QCPE, 1987, 544.
79. Spangler, D.; Williams, I. H.; Maagiora, G. J. Comput. Chem. 1983, 4, 524.
80. Binkley, J. S.; Pople, J. A.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 939.
81. Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2252.
82. Allen, M. P.; Tildesley, D. J. Computer Simulation of Liquids; Clarendon: Oxford, UK, 1987.
83. Shavitt, I. In Methods of Electronic Structure Theory; Schaefer, H. F., III, Ed.; Plenum: New York, 1977.
84. Dunnina, T. H.; Hay, P. J. In Methods of Electronic Structure Theory, Schaefer, H. F., III, Ed.; Plenum: New York, 1977.
85. Lanehoff, S. R.; Davidson, E. R. Int. J. Quantum Chem. 1974, 8, 61.
86. 2O complex by larger CI(SD) in the "split-valence" CI space with no frozen core Orbitals (10 electrons in 24 orbitals). The number of configuration state functions is 10011. As expected, this extensive account of the electron correlation effects stabilizes the covalent structure compared to the ionic one, which turns out to contribute essentially to the resultant endothermicity of the first PT step.
87. Jorgensen, W. L.; Chandrasekhar, J.; Madura, J.; Impey, R. W.; Klein, M. L. J. Chem. Phys. 1983, 79, 926.
88. Moøller, C.; Plesset, M. S. Phys. Rev. 1934, 45, 618.
89. Krishnan, R.; Frisch, M. J.; Pople, J. A. J. Chem. Phys. 1980, 72, 4244.
90. Clementi, E.; Barsotti, R. Chem. Phys. Lett. 1980, 59, 21.
91. Mezei, M.; Beveridge, D. L. J. Chem. Phys. 1981, 74, 6902.
92. Szasz, G. I.; Heinzinger, K. Z Naturforsh., A 1979, 34, 840.
93. Impey, R. W.; Madden, P. A.; McDonald, I. R. J. Phys. Chem. 1983, 87, 5071.
94. Chandrasekhar, J.; Spellmeyer, D. C.; Jorgensen, W. L. J. Am. Chem. Soc. 1984, 106, 903.
95. j; coordinates are used first for the determination of the charge parameters (Table 1) and then for the MC simulations, both of which would not be quite sensitive to the slight arbitrariness of the proton position.
96. The coordinates R, were fixed in the MC simulations. All of the three potentials V, (i = 1-3) were computed at every MC step, one of which or a linear combination of the two is referred to for the Metropolis sampling test.
97. Ando, K.; Kato, S. J. Chem. Phys. 1991, 95, 5966. .
98. 2) under the influence of classical electrostatic field from the point charges of ∼ 130 TIP3P waters within the potential cut-off sphere in the simulation box sampled in the course of the MC simulation. The coordinates of the three hydrogen atoms other than the transferring two protons in the solute 1-3 were not optimized in the computation of the potential surfaces (because geometry optimization under classical external point charges can be misleading). This may cause slight structural strain in the ionic states and thus small overestimate of the energy difference between the neutral and ionic states. However, we have expected error cancellation between this and small overstabilization of the ionic states in the simulation due to the RHF approximation employed for the charge determination. These two factors always tend to cancel each other rather than to accumulate. As mentioned in ref 42, very large calculations (of energy gradient and electron correlation) on a larger hydration cluster would be needed to qualify this issue.
99. We first fitted the simulation data of the free energy curves to two parabolas of an equal curvature, from which the solvent reorganization energy was calculated. The nns deviation of the fitting was about 0.9 kcal/ mol.
100. This situation could be quite different in a small gas phase cluster situation as opposed to the present solution study. In the former, the bodily motion of e.g. a single solvating water molecule in switching its solvation from one of the reactant partners to another is quite important (see: Beksic, D.; Bertran, J.; Luch, J. M.; Hynes, J. T. J. Phys. Chem. A 1998, 702, 3977);
101. in the present solution case, as in previous HC1 studies (refs 10 and 11), small librational adjustments are involved with the nuclear center of masses of the solvating waters largely in place. It is also of interest to note that if the proton were to be treated (inappropriately) as a classical particle, then a variable more akin to a spatial gradient of AE would play a role (Hynes, J. T. In Simon, J. D., Ed.: Ultrafast Dynamics of Chemical Systems; Kluwer: Dordrecht, The Netherlands, 1994).
102. 12 is described by an interpolation method outlined in the Appendix.
103. 12‡ presented here is updated by improved (interpolation) calculations from the previous report in ref 12.
104. Hammond, G. S. J. Am. Chem. Soc. 1955, 77, 334.
105. Pross, A. Adv. Phys. Org. Chem. 1977, I, 69.
106. Kiefer, P.; Hynes, J. T. Manuscript in preparation.
107. This denotes the mean-field parametrization of the electronic polarization of the TIP3P model for bulk water. We should also note that the nonpolarizable solvent models tend to overestimate the solvent reorganization energy. See e.g. ref 9.
108. Agmon, N. Chem. Phys. Lett. 1995, 244, 456;
109. J. Chim. Phys. (Paris) 1996, 93, 1114.
110. Newton, M. D. J. Chem. Phys. 1977, 67, 5535.
111. Reed, A. E.; Weinhold, F. J. Chem. Phys. 1983, 78, 4066.
112. Reed, A. E.; Weinstock, R. B.; Weinhold F. J. Chem. Phys. 1985, 83, 735.
113. +.
114. The Monte Carlo sampled points of the free energy curves are again well approximated by parabolas with the rms deviation of 1.1 kcal/mol.
115. - ion nearby, which can assist in localizing the proton compared to the case of proton transport in bulk water.
116. Here we limit ourselves to a diabatic treatment, which is sufficient to clarify the issue.
117. 0 is smaller than the reorganization energy.
118. Antonchenko, V. Ya.; Davydov, A. S.; Zolotariuk, A. V. Phys. Status. Solidi B 1983, 115, 631.
119. Davydov, A. S. Solitons in molecular systems;, Naukovaja Dumka: Kiev, Ukraine, 1984.
120. Godzik, A. Chem. Phys. Lett. 1990, 171, 217.
121. For some recent reviews, see the articles by: Kryachko E. S.; Sokhan, V. P. In ref 2b; Nagle, J. F. In ref 2b.
122. The spectroscopic argument of ref 17 used to support the inherent stability of a contact ion pair for HF in water will be discussed elsewhere (ref 64a).
123. Hammes-Schiffer, S.; Tully, J. C. J. Chem. Phys. 1995, 103, 8525;
124. J. Phys. Chem. 1995, 99, 5793.
125. (a) Schroeder, T.; Staib, A.; Hynes, J. T. Work in progress.
126. (b) Ando, K.; Staib, A.; Hynes, J. T. In Femtochemistry: Ultrafast Chemical and Physical Processes in Molecular Systems; Chergui, M., Ed.; World Scientific: Singapore, 1996; p 534.
127. Tramer, A., Ed. Fast Elementary Processes in Chemical and Biological Systems; AIP: New York, 1996; p 326.
128. Luz, Z.; Meiboom, S. J. Am. Chem. Soc. 1964, 86, 4768.
129. -1 (from the electrical mobility measurements), we obtain the recombination distance of 8.2 Å.
130. Additional support, in the different context of halide ion-water comples IR spectra (Ayotte, P.; Bailey, C. G.; Weddle, G. H.; Johnson, M. A. J. Phys. Chem. A 1998, 102, 3067)
131. can be found (Thompson, W. H.; Hynes, J. T. Unpublished work).