Molecular mechanism of HCl acid ionization in water: Ab initio potential energy surfaces and Monte Carlo simulations

Journal of Physical Chemistry B

Volumn 101, Issue 49, 1997, Pages 10464-10478

  Ando, Koji ^a,b   Hynes, James T ^a  

^a UNIVERSITY OF COLORADO   (United States)

^b UNIVERSITY OF TSUKUBA   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE TRANSFER; COMPUTER SIMULATION; ELECTRONIC STRUCTURE; FREE ENERGY; HYDROCHLORIC ACID; MOLECULAR DYNAMICS; MONTE CARLO METHODS; POLARIZATION; PROTONS; SOLVENTS;

ACID IONIZATION; MOLECULAR ORBITALS; POTENTIAL ENERGY SURFACES;

IONIZATION OF LIQUIDS;

EID: 0031553352     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp970173j     Document Type: Article

References (204)

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118. ij, independent of whether the probability distribution is Gaussian or not. Thus, the curvatures of the two diabatic free energy curves must be the same when they are parabolic. See: Kakitani, T.; Mataga, N. J. Phys. Chem. 1985, 89, 4752. Carter, E. A.; Hynes, J. T. Ibid. 1989, 93, 2184. Tachiya, M. Ibid. 1989, 93, 7050. Yoshimori, A.; Kakitani, T.; Enomoto, Y.; Mataga, N. Ibid. 1989, 93, 8316. See also ref 48 for simulation studies and the following for connections to solvation free energies: Fonseca, T.; Ladanyi, B. M.; Hynes, J. T. J. Phys. Chem. 1992, 96, 4085.
119. ij, independent of whether the probability distribution is Gaussian or not. Thus, the curvatures of the two diabatic free energy curves must be the same when they are parabolic. See: Kakitani, T.; Mataga, N. J. Phys. Chem. 1985, 89, 4752. Carter, E. A.; Hynes, J. T. Ibid. 1989, 93, 2184. Tachiya, M. Ibid. 1989, 93, 7050. Yoshimori, A.; Kakitani, T.; Enomoto, Y.; Mataga, N. Ibid. 1989, 93, 8316. See also ref 48 for simulation studies and the following for connections to solvation free energies: Fonseca, T.; Ladanyi, B. M.; Hynes, J. T. J. Phys. Chem. 1992, 96, 4085.
120. ij, independent of whether the probability distribution is Gaussian or not. Thus, the curvatures of the two diabatic free energy curves must be the same when they are parabolic. See: Kakitani, T.; Mataga, N. J. Phys. Chem. 1985, 89, 4752. Carter, E. A.; Hynes, J. T. Ibid. 1989, 93, 2184. Tachiya, M. Ibid. 1989, 93, 7050. Yoshimori, A.; Kakitani, T.; Enomoto, Y.; Mataga, N. Ibid. 1989, 93, 8316. See also ref 48 for simulation studies and the following for connections to solvation free energies: Fonseca, T.; Ladanyi, B. M.; Hynes, J. T. J. Phys. Chem. 1992, 96, 4085.
121. ij, independent of whether the probability distribution is Gaussian or not. Thus, the curvatures of the two diabatic free energy curves must be the same when they are parabolic. See: Kakitani, T.; Mataga, N. J. Phys. Chem. 1985, 89, 4752. Carter, E. A.; Hynes, J. T. Ibid. 1989, 93, 2184. Tachiya, M. Ibid. 1989, 93, 7050. Yoshimori, A.; Kakitani, T.; Enomoto, Y.; Mataga, N. Ibid. 1989, 93, 8316. See also ref 48 for simulation studies and the following for connections to solvation free energies: Fonseca, T.; Ladanyi, B. M.; Hynes, J. T. J. Phys. Chem. 1992, 96, 4085.
122. ij, independent of whether the probability distribution is Gaussian or not. Thus, the curvatures of the two diabatic free energy curves must be the same when they are parabolic. See: Kakitani, T.; Mataga, N. J. Phys. Chem. 1985, 89, 4752. Carter, E. A.; Hynes, J. T. Ibid. 1989, 93, 2184. Tachiya, M. Ibid. 1989, 93, 7050. Yoshimori, A.; Kakitani, T.; Enomoto, Y.; Mataga, N. Ibid. 1989, 93, 8316. See also ref 48 for simulation studies and the following for connections to solvation free energies: Fonseca, T.; Ladanyi, B. M.; Hynes, J. T. J. Phys. Chem. 1992, 96, 4085.
123. Non-Gaussian statistics might be important for proton transfer cases compared to electron transfer cases, due to the longer-ranged electrostatic potentials of the latter. The deviation from Gaussian behavior of the diabatic curses - the rms deviation of the Monte Carlo points from the fitted parabolas - found in the present system is as small as the simulation uncertainties (≲ 1 kcal/mol), which implies that the present system cannot be very non-Gaussian. But it should be noted that the harmonic diabatic curves are here used only as a guide to the ultimate calculation of the free energy curves.
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126. In simple VB terms (ref 7), this is due to the exponential dependence of the overlap between atomic orbitals, and thus the electronic coupling between VB states, on the internuclear distance.
127. 1, the length ratio of the ordinate and abscissa of Figure 7 is scaled to be about 15:1. This further supports the adequacy of the quantum adiabatic separation of the proton coordinate.
128. 1 in a weakly exothermic reaction. This is precisely the direction consistent with our present TS location, for a much more exothermic reaction. This strongly suggests to us that an alternative qcmf approach would also find the present TS, but this awaits subsequent confirmation.
129. Another possible consequence of the quantum character of the solvent (librational) motion would be its tunneling through the barrier of the solvent free energy curves. This is not important for the first proton transfer step because the barrier is low. The effect on the second step may be considered within the harmonic bath model (e.g. ref 18a). We feel, however, that these may be considered as separate issues from the adiabatic separation approximation between the proton and the solvent coordinates.
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137. Del Bene, J. E.; Frisch, M. J.; Luke, B. T.; Pople, J. A. J. Phys. Chem. 1983, 87, 3279. Frisch, M. J.; Pople, J. A.; Del Bene, J. E. Ibid. 1985, 89, 3664. Del Bene, J. E.; Frisch, M. J.; Pople, J. A. Ibid. 1985, 89, 3669. Clementi, E. Ibid. 1985, 89, 4426.
138. Del Bene, J. E.; Frisch, M. J.; Luke, B. T.; Pople, J. A. J. Phys. Chem. 1983, 87, 3279. Frisch, M. J.; Pople, J. A.; Del Bene, J. E. Ibid. 1985, 89, 3664. Del Bene, J. E.; Frisch, M. J.; Pople, J. A. Ibid. 1985, 89, 3669. Clementi, E. Ibid. 1985, 89, 4426.
139. Del Bene, J. E.; Frisch, M. J.; Luke, B. T.; Pople, J. A. J. Phys. Chem. 1983, 87, 3279. Frisch, M. J.; Pople, J. A.; Del Bene, J. E. Ibid. 1985, 89, 3664. Del Bene, J. E.; Frisch, M. J.; Pople, J. A. Ibid. 1985, 89, 3669. Clementi, E. Ibid. 1985, 89, 4426.
140. Similar kind of solvent motion in the second hydration shell has been suggested in a very recent ab initio molecular dynamics simulation work of a classical proton dynamics in 32 water molecules. Tuckerman, M. E.; Laasonen, K.; Sprik, M.; Parrinello, M. J. Chem. Phys. 1995, 103, 105; J. Phys. Chem. 1995, 99, 5749. For a review, see: Tuckerman, M. E.; Ungar, P. J.; von Rosenvinge, T.; Klein, M. L. Ibid. 1996, 100, 12878. See also a consideration in: Agmon, N. Chem. Phys. Lett. 1995, 244, 456.
141. Similar kind of solvent motion in the second hydration shell has been suggested in a very recent ab initio molecular dynamics simulation work of a classical proton dynamics in 32 water molecules. Tuckerman, M. E.; Laasonen, K.; Sprik, M.; Parrinello, M. J. Chem. Phys. 1995, 103, 105; J. Phys. Chem. 1995, 99, 5749. For a review, see: Tuckerman, M. E.; Ungar, P. J.; von Rosenvinge, T.; Klein, M. L. Ibid. 1996, 100, 12878. See also a consideration in: Agmon, N. Chem. Phys. Lett. 1995, 244, 456.
142. Similar kind of solvent motion in the second hydration shell has been suggested in a very recent ab initio molecular dynamics simulation work of a classical proton dynamics in 32 water molecules. Tuckerman, M. E.; Laasonen, K.; Sprik, M.; Parrinello, M. J. Chem. Phys. 1995, 103, 105; J. Phys. Chem. 1995, 99, 5749. For a review, see: Tuckerman, M. E.; Ungar, P. J.; von Rosenvinge, T.; Klein, M. L. Ibid. 1996, 100, 12878. See also a consideration in: Agmon, N. Chem. Phys. Lett. 1995, 244, 456.
143. Similar kind of solvent motion in the second hydration shell has been suggested in a very recent ab initio molecular dynamics simulation work of a classical proton dynamics in 32 water molecules. Tuckerman, M. E.; Laasonen, K.; Sprik, M.; Parrinello, M. J. Chem. Phys. 1995, 103, 105; J. Phys. Chem. 1995, 99, 5749. For a review, see: Tuckerman, M. E.; Ungar, P. J.; von Rosenvinge, T.; Klein, M. L. Ibid. 1996, 100, 12878. See also a consideration in: Agmon, N. Chem. Phys. Lett. 1995, 244, 456.
144. Hückel, Bernal, and Fowler and Conway et al. suggested that the proton transport in water is controlled by the rotation of a water molecule. The rotational motion implied or indicated there is that of the proton-accepting water molecule and is different from that identified here. Hückel, E. Z. Elektrochem. 1928, 34, 546. Bernal, J. D.; Fowler, R. H. J. Chem. Phys. 1933, 1, 515. Conway, B. E.; Bockris, J. O'M.; Linton, H. J. Chem. Phys. 1956, 24, 834.
145. Hückel, Bernal, and Fowler and Conway et al. suggested that the proton transport in water is controlled by the rotation of a water molecule. The rotational motion implied or indicated there is that of the proton-accepting water molecule and is different from that identified here. Hückel, E. Z. Elektrochem. 1928, 34, 546. Bernal, J. D.; Fowler, R. H. J. Chem. Phys. 1933, 1, 515. Conway, B. E.; Bockris, J. O'M.; Linton, H. J. Chem. Phys. 1956, 24, 834.
146. Hückel, Bernal, and Fowler and Conway et al. suggested that the proton transport in water is controlled by the rotation of a water molecule. The rotational motion implied or indicated there is that of the proton-accepting water molecule and is different from that identified here. Hückel, E. Z. Elektrochem. 1928, 34, 546. Bernal, J. D.; Fowler, R. H. J. Chem. Phys. 1933, 1, 515. Conway, B. E.; Bockris, J. O'M.; Linton, H. J. Chem. Phys. 1956, 24, 834.
147. 2O system in pure water, with attention to the influence of the O-O distance, include in addition to refs 23 and 24: Janoschek, R.; Weidemann, E. G.; Pfeiffer, H.; Zundel, G. J. Am. Chem. Soc. 1972, 94, 2387. Muñiz, A. M.; Bertrán, J.; Andrés, J. L.; Duran, M.; Lledós, A. J. Chem. Soc., Faraday Trans. 1 1985, 81, 1547.
148. 2O system in pure water, with attention to the influence of the O-O distance, include in addition to refs 23 and 24: Janoschek, R.; Weidemann, E. G.; Pfeiffer, H.; Zundel, G. J. Am. Chem. Soc. 1972, 94, 2387. Muñiz, A. M.; Bertrán, J.; Andrés, J. L.; Duran, M.; Lledós, A. J. Chem. Soc., Faraday Trans. 1 1985, 81, 1547.
149. a ∼ -19).
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155. For a discussion of these issues, see also: Gehlen, J. N.; Chandler, D.; Kim, H. J.; Hynes, J. T. J. Phys. Chem. 1992, 96, 1748. Gehlen, J. N.; Chandler, D. J. Chem. Phys. 1992, 97, 4958. Kim, H. J.; Bianco, R.; Gertner, B. J.; Hynes, J. T. J. Phys. Chem. 1993, 97, 1723.
156. For a discussion of these issues, see also: Gehlen, J. N.; Chandler, D.; Kim, H. J.; Hynes, J. T. J. Phys. Chem. 1992, 96, 1748. Gehlen, J. N.; Chandler, D. J. Chem. Phys. 1992, 97, 4958. Kim, H. J.; Bianco, R.; Gertner, B. J.; Hynes, J. T. J. Phys. Chem. 1993, 97, 1723.
157. For a discussion of these issues, see also: Gehlen, J. N.; Chandler, D.; Kim, H. J.; Hynes, J. T. J. Phys. Chem. 1992, 96, 1748. Gehlen, J. N.; Chandler, D. J. Chem. Phys. 1992, 97, 4958. Kim, H. J.; Bianco, R.; Gertner, B. J.; Hynes, J. T. J. Phys. Chem. 1993, 97, 1723.
158. For the solvent electronic polarization effects on proton transfer potentials from an alternative viewpoint, see the path integral quantum Monte Carlo study in ref 18b.
159. r = 12.6 kcal/mol, we obtain 1.4 kcal/mol as an estimate for the barrier height lowering for the first proton transfer step. As a result, the ground and the first excited proton vibrational levels are lowered by 0.66 and 0.24 kcal/mol, respectively. As discussed in text, the former will reduce the net reaction barrier. (See ref 9 for related results.)
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163. -1 to evaluate the parameters in Table 3. See ref 48b for an evaluation of this frequency by a molecular dynamics simulation and for an examination of the linear response assumption.
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166. Hynes, J. T. In The Theory of Chemical Reaction Dynamics; Baer, M., Ed.; CRC: Boca Raton, FL, 1985; Vol. 4. Truhlar, D. G.; Hase, W. L.; Hynes, J. T. J. Phys. Chem. 1983, 87, 2664. Whitnell, R. M.; Wilson, K. R. Adv. Comput. Chem. 1993, 4, 67. Hänggi, P.; Talkner, P.; Borkovec, M. Rec. Mod. Phys. 1990, 62, 250. Nitzan, A. Adv. Chem. Phys. 1988, 70, 489, Part 2. Berne, B. J.; Borkovec, M.; Straub, J. E. J. Phys. Chem. 1988, 92, 3711. Truhlar, D. G.; Garrett, B. C.; Klippenstein, S. J. Ibid. 1996, 100, 12771. Voth, G. A.; Hochstrasser, R. M. Ibid. 1996, 100, 13034.
167. Hynes, J. T. In The Theory of Chemical Reaction Dynamics; Baer, M., Ed.; CRC: Boca Raton, FL, 1985; Vol. 4. Truhlar, D. G.; Hase, W. L.; Hynes, J. T. J. Phys. Chem. 1983, 87, 2664. Whitnell, R. M.; Wilson, K. R. Adv. Comput. Chem. 1993, 4, 67. Hänggi, P.; Talkner, P.; Borkovec, M. Rec. Mod. Phys. 1990, 62, 250. Nitzan, A. Adv. Chem. Phys. 1988, 70, 489, Part 2. Berne, B. J.; Borkovec, M.; Straub, J. E. J. Phys. Chem. 1988, 92, 3711. Truhlar, D. G.; Garrett, B. C.; Klippenstein, S. J. Ibid. 1996, 100, 12771. Voth, G. A.; Hochstrasser, R. M. Ibid. 1996, 100, 13034.
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176. - ion, this will have to await calculations on the proton transport in water using the same potential functions.
177. This is a very simplified statement, since we have found a certain amount of charge delocalization in the contact ion pair state (cf. Table 1). Further, the hydration states of the contact and the solvent-separated ion pairs (2 and 3) differ from a complete first solvation shell situation.
178. There are no experimental results on HCl ionization time scales for, e.g., the first step; see below.
179. -1 (Okumura, M.; Yeh, L. I.; Myers, J. D.; Lee, Y. T. J. Phys. Chem. 1990, 94, 3416), respectively].
180. See: Fonseca, T. J. Chem. Phys. 1989, 91, 2869 and references therein. The estimate in the present work for the 2 → 3 solvent barrier is on the very edge for the existence of a well-defined rate constant. The considerations of section VI suggest that the solvent coordinate barrier is even lower and nonexponential kinetics seem likely.
181. We thank Professor A. Zewail for a discussion of a possibly similar situation in an excited electronic state organic acid proton transfer.
182. n cluster may not have the favorable sequencing and geometry of the cluster examined in section II.B.
183. This basic conclusion is also reached via quite different techniques in: Laasonen, K.; Klein, M. L. J. Am. Chem. So. 1994, 116, 11620.
184. See, e.g., the articles in: Ultrafast Dynamics of Chemical Systems; Simon, J. D., Ed.; Kluwer Academic Publishers: Dordrecht, 1994. Ultrafast Reaction Dynamics and Solvent Effects; Gauduel, Y., Rossky, P. J., Eds.; AIP Press: New York, 1994. For a recent review on solvation dynamics, see e.g.: Stratt, R. M.; Maroncelli, M. J. Phys. Chem. 1996, 100, 12981.
185. See, e.g., the articles in: Ultrafast Dynamics of Chemical Systems; Simon, J. D., Ed.; Kluwer Academic Publishers: Dordrecht, 1994. Ultrafast Reaction Dynamics and Solvent Effects; Gauduel, Y., Rossky, P. J., Eds.; AIP Press: New York, 1994. For a recent review on solvation dynamics, see e.g.: Stratt, R. M.; Maroncelli, M. J. Phys. Chem. 1996, 100, 12981.
186. See, e.g., the articles in: Ultrafast Dynamics of Chemical Systems; Simon, J. D., Ed.; Kluwer Academic Publishers: Dordrecht, 1994. Ultrafast Reaction Dynamics and Solvent Effects; Gauduel, Y., Rossky, P. J., Eds.; AIP Press: New York, 1994. For a recent review on solvation dynamics, see e.g.: Stratt, R. M.; Maroncelli, M. J. Phys. Chem. 1996, 100, 12981.
187. A simulation study on the acidity of HCl relative to water in ambient and supercritical water is recently performed in: Balbuena, P. B.; Johnston, K. P.; Rossky, P. J. J. Phys. Chem. 1996, 100, 2716.
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190. For a related phenomenon for NaCl ionization, see: Gao, J. J. Phys. Chem. 1994, 98, 6049. Cui, S. T.; Harris, J. G. Chem. Eng. Sci., in press.
191. For a related phenomenon for NaCl ionization, see: Gao, J. J. Phys. Chem. 1994, 98, 6049. Cui, S. T.; Harris, J. G. Chem. Eng. Sci., in press.
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