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Microhydration effects on a model SN2 reaction in a nonpolar solvent

J. Chem. Phys. 130, 194502 (2009); doi:10.1063/1.3138902

Published 15 May 2009

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Katherine V. Nelson and Ilan Benjamin
Department of Chemistry and Biochemistry, University of California, Santa Cruz, California 95064, USA
Using a recently developed empirical valence bond model for the nucleophilic substitution reaction (SN2) in solution, we examine microhydration effects on the benchmark Cl−+CH3Cl reaction in liquid chloroform. Specifically, the effect of the hydration of the reactive system by one to five water molecules on the reaction-free energy profile and the rate constant is examined. We find that the activation-free energy is highly sensitive to the number of water molecules hydrating the nucleophile, increasing the barrier by about 4 kcal/mol by the first water molecule. With five water molecules, the barrier height is 10 kcal/mol larger than the barrier in bulk chloroform and only 3 kcal/mol below the barrier in bulk water. A number of properties vary monotonically with the number of water molecules, including the rate of change in the system's electronic structure and the solvent stabilization of the transition state. These and other properties are a rapidly varying function of the reaction coordinate. Deviation from transition state theory due to barrier recrossing is not large and falls between the behavior in bulk water and bulk chloroform. ©2009 American Institute of Physics
History: Received 19 March 2009; accepted 29 April 2009; published 15 May 2009
Permalink: http://link.aip.org/link/?JCPSA6/130/194502/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.30.Nr
    Association, addition, insertion, cluster formation (chemical reactions)
  • 82.30.Rs
    Hydrogen bonding, hydrophilic effects (chemical reactions)
  • 82.30.Hk
    Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange)
  • 82.20.Db
    Transition state theory and statistical theories of rate constants (chemical kinetics)
  • 82.20.Pm
    Chemical rate constants, reaction cross sections, and activation energies
  • 82.20.Yn
    Solvent effects on reactivity in chemical kinetics
  • 82.30.Fi
    Ion-molecule, ion-ion, and charge-transfer chemical reactions
  • 82.60.-s
    Chemical thermodynamics
  • YEAR: 2009

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (57)
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  1. C. K. Ingold, Structure and Mechanism in Organic Chemistry, 2nd ed. (Cornell University, Ithaca, NY, 1969).
  2. A. Warshel and R. M. Weiss, J. Am. Chem. Soc. 102, 6218 (1980).
  3. J. K. Hwang, G. King, S. Creighton, and A. Warshel, J. Am. Chem. Soc. 110, 5297 (1988).
  4. J. Chandrasekhar, S. F. Smith, and W. L. Jorgensen, J. Am. Chem. Soc. 106, 3049 (1984).
  5. W. L. Jorgensen and J. K. Buckner, J. Phys. Chem. 90, 4651 (1986).
  6. C. Reichardt, Solvents and Solvent Effects in Organic Chemistry, 2nd ed. (Springer-Verlag, Weinheim, 1988).
  7. J. R. Mathis, R. Bianco, and J. T. Hynes, J. Mol. Liq. 61, 81 (1994).
  8. J. Villa, J. Bentzien, A. Gonzalez-Lafont, J. M. Lluch, J. Bertran, and A. Warshel, J. Comput. Chem. 21, 607 (2000).
  9. X. G. Zhao, D. H. Lu, Y. P. Liu, G. C. Lynch, and D. G. Truhlar, J. Chem. Phys. 97, 6369 (1992).
  10. Y. Okuno, J. Chem. Phys. 105, 5817 (1996).
  11. M. Re and D. Laria, J. Chem. Phys. 105, 4584 (1996).
  12. A. A. Mohamed and F. Jensen, J. Phys. Chem. A 105, 3259 (2001).
  13. P. B. Balbuena, K. P. Johnston, and P. J. Rossky, J. Am. Chem. Soc. 116, 2689 (1994).
  14. P. B. Balbuena, K. P. Johnston, and P. J. Rossky, J. Phys. Chem. 99, 1554 (1995).
  15. G. E. Bennett, P. J. Rossky, and K. P. Johnston, J. Phys. Chem. 99, 16136 (1995).
  16. L. W. Flanagin, P. B. Balbuena, K. P. Johnston, and P. J. Rossky, J. Phys. Chem. 99, 5196 (1995).
  17. C. S. Pomelli and J. Tomasi, J. Phys. Chem. A 101, 3561 (1997).
  18. M. H. M. Olsson and A. Warshel, J. Am. Chem. Soc. 126, 15167 (2004).
  19. J. E. Klijn and J. B. F. N. Engberts, Langmuir 21, 9809 (2005).
  20. D. Landini, A. Maia, and A. Rampoldi, J. Org. Chem. 54, 328 (1989).
  21. A. Maia, Pure Appl. Chem. 67, 697 (1995).
  22. D. Albanese, D. Landini, A. Maia, and M. Penso, Ind. Eng. Chem. Res. 40, 2396 (2001).
  23. C. M. Starks, C. L. Liotta, and M. Halpern, Phase Transfer Catalysis (Chapman and Hall, New York, 1994).
  24. Y. H. Shao, M. V. Mirkin, and J. F. Rusling, J. Phys. Chem. B 101, 3202 (1997).
  25. M. Makosza, Pure Appl. Chem. 72, 1399 (2000).
  26. D. Albanese, Catal. Rev. - Sci. Eng. 45, 369 (2003).
  27. Interfacial Catalysis, edited by A. G. Volkov (Dekker, New York, 2003).
  28. C. A. Eckert, C. L. Liotta, D. Bush, J. S. Brown, and J. P. Hallett, J. Phys. Chem. B 108, 18108 (2004).
  29. D. K. Bohme and A. B. Raksit, Can. J. Chem. 63, 3007 (1985).
  30. X. G. Zhao, S. C. Tucker, and D. G. Truhlar, J. Am. Chem. Soc. 113, 826 (1991).
  31. J. M. Hayes and S. M. Bachrach, J. Phys. Chem. A 107, 7952 (2003).
  32. J. R. Pliego, J. Phys. Chem. B 113, 505 (2009).
  33. I. Benjamin, J. Chem. Phys. 129, 074508 (2008).
  34. J. P. Bergsma, B. J. Gertner, K. R. Wilson, and J. T. Hynes, J. Chem. Phys. 86, 1356 (1987).
  35. S. E. Huston, P. J. Rossky, and D. A. Zichi, J. Am. Chem. Soc. 111, 5680 (1989).
  36. J. L. Gao, J. Am. Chem. Soc. 113, 7796 (1991).
  37. Y. J. Cho, S. R. Vandelinde, L. Zhu, and W. L. Hase, J. Chem. Phys. 96, 8275 (1992).
  38. R. Bianco, S. Miertus, M. Persico, and J. Tomasi, Chem. Phys. 168, 281 (1992).
  39. M. Aguilar, R. Bianco, S. Miertus, M. Persico, and J. Tomasi, Chem. Phys. 174, 397 (1993).
  40. M. Sato, H. Yamataka, Y. Komeiji, Y. Mochizuki, T. Ishikawa, and T. Nakano, J. Am. Chem. Soc. 130, 2396 (2008).
  41. S. C. Tucker and D. G. Truhlar, J. Am. Chem. Soc. 112, 3338 (1990).
  42. J. -P. Hansen and I. R. McDonald, Theory of Simple Liquids, 2nd ed. (Academic, London, 1986).
  43. A. L. McClellan, Tables of Experimental Dipole Moments (Freeman, San Francisco, 1963).
  44. I. Benjamin, J. Chem. Phys. 103, 2459 (1995).
  45. T. M. Chang and L. X. Dang, J. Phys. Chem. B 101, 10518 (1997).
  46. T. M. Chang, L. X. Dang, and K. A. Peterson, J. Phys. Chem. B 101, 3413 (1997).
  47. J. I. Timoneda and J. T. Hynes, J. Phys. Chem. 95, 10431 (1991).
  48. R. S. Mulliken, C. A. Rieke, D. Orloff, and H. Orloff, J. Chem. Phys. 17, 1248 (1949).
  49. D. Chandler, Introduction to Modern Statistical Mechanics (Oxford University Press, Oxford, 1987).
  50. G. King and A. Warshel, J. Chem. Phys. 93, 8682 (1990).
  51. B. J. Berne, M. Borkovec, and J. E. Straub, J. Phys. Chem. 92, 3711 (1988).
  52. B. J. Gertner, K. R. Wilson, and J. T. Hynes, J. Chem. Phys. 90, 3537 (1989).
  53. R. M. Whitnell and K. R. Wilson, in Reviews in Computational Chemistry, edited by K. B. Lipkowitz and D. B. Boyd (VCH, New York, 1993).
  54. M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids (Clarendon, Oxford, 1987).
  55. B. J. Gertner, J. P. Bergsma, K. R. Wilson, S. Lee, and J. T. Hynes, J. Chem. Phys. 86, 1377 (1987).
  56. J. T. Hynes, in The Theory of Chemical Reactions, edited by M. Baer (CRC, Boca Raton, FL, 1985), Vol. 4, p. 171.
  57. J. P. Bergsma, B. J. Gertner, K. R. Wilson, and J. T. Hynes, J. Chem. Phys. 86, 1356 (1987).

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