Kinetics of the proton transfer in X⋯(H2O)4 clusters (X = H2O, NH3, H2S, and HCl): Evidence of a concerted mechanism

Journal of Physical Chemistry

Volumn 100, Issue 41, 1996, Pages 16495-16501

  Planas, Marc ^a   Lee, Chengteh ^b   Novoa, Juan J ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

^b Premis Corporation   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000202782     PISSN: 00223654     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp960789t     Document Type: Article

References (34)

1. For a general introduction see for instance: Bell, R. P. The Proton in Chemistry, 2nd ed.; Chapman and Hall: London, 1973.
2. Proton Transfer in Hydrogen-Bonded Systems; Bountis, T., Ed.; Plenum: New York, 1993.
3. Eigen, D. Angew. Chem., Int. Ed. Engl. 1964, 3, 1.
4. Albery, W. J. Prog. React. Kinet. 1967, 4, 353.
5. Crooks, J. E. Compr. Chem. Kinet. 1977, 8, 197.
6. Somasundram, K.; Amos, R. D.; Handy, N. C. Theor. Chim. Acta 1986, 69, 491.
7. Del Bene, J. E. J. Phys. Chem. 1988, 92, 2874.
8. Theoretical: Bacskay, G. B. Mol. Phys. 1992, 77, 61.
9. Experimental: Legon, A. C.; Willoughby, L. G. Chem. Phys. Lett. 1983, 95, 449.
10. Ando, K.; Hynes, J. T. In Structure and Reactivity in Aqueous Solutions; ACS Symposium Series Vol. 568; Cramer, C. J., Truhlar, D. G., Eds.; American Chemical Society: Washington, DC, 1994, and references therein.
11. Ando, K.; Hynes, J. T. J. Mol. Liq. 1995, 64, 25.
12. Rivail, J. L.; Antonczak, S.; Chipot, C.; Ruiz-Lopez, M. F.; Gorb, L. G. In Structure and Reactivity in Aqueous Solutions; ACS Symposium Series Vol. 568; Cramer, C. J., Truhlar, D. G., Eds.; American Chemical Society: Washington, DC, 1994.
13. Waldron, R. D.; Hornig, D. F. J. Am. Chem. Soc. 1953, 75, 6079.
14. Lee, C.; Sosa, C.; Novoa, J. J. J. Chem. Phys. 1995, 103, 4360.
15. Lee, C.; Sosa, C.; Planas, M.; Novoa, J. J. J. Chem. Phys. 1996, 104, 70.
16. Lee, C.; Fitzgerald, G.; Planas, M.; Novoa, J. J. J. Phys. Chem. 1996, 100, 7398.
17. Scrocco, E.; Tomasi, J. Adv. Quantum Chem. 1978, 11, 115.
18. Politzer, P.; Murray, J. S. Rev. Comput. Chem. 1991, 2, 273.
19. Tozer, D. J.; Lee, C.; Fitzgerald, G. J. Chem. Phys. 1996, 104, 5555.
20. Becke, A. D. Phys. Rev. A 1988, 38, 3098.
21. Becke, A. D. J. Chem. Phys. 1992, 96, 2155.
22. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
23. Parr, R. G.; Yang, W. Density-Fuctional Weary of Atoms; Oxford Science Publications: New York, 1989.
24. Kim, K.; Jordan, K. D. J. Phys. Chem. 1994, 98, 10089.
25. Novoa, J. J.; Sosa, C. J. Phys. Chem. 1995, 99, 15837.
26. Lee, C.; Stahlberg, E.; Fitzgerald, G. J. Phys. Chem., submitted.
27. DGauss is a software product available from Cray Research Inc., a part of the UniChem software package. For details of the Dgauss methodology see: Andzelm, J.; Wimmer, E. J. Chem. Phys. 1992, 96, 1280.
28. Gaussian 94, Revision C.3: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Peterson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Ciolowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D., J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A., Gaussian, Inc., Pittsburgh, PA, 1995.
29. Bernardi, F.; Robb, M. A. Adv. Chem. Phys. 1987, 67, 155.
30. There is some ambiguity in defining the fragments at the transition state geometry, because the proton being transferred can be associated with any of the two fragments to which it is connected. To solve this ambiguity, we have assigned the proton to the fragment to which is closer. As in the clusters studied here, the transition states are all closer to the products with structures similar to that for the product, the positive charge is located on the proton being transferred, and the transition state is doubly charged.
31. Abkowicz, A. J.; Latajka, Z.; Scheiner, S.; Chalasinski, G. J. Mol. Struct.: THEOCHEM 1995, 342, 153.
32. The BSSE was also be computed for the neutral fragment and is 2.1 kcal/mol. However in this case, the monomers are different to the ionic fragments used to compute the BSSE for the double ionic and transition state clusters. This can create some inconsistencies in the BSSE computed values, as have been already indicated in the literature (see ref 24, for example).
33. Turi, L.; Dannenberg, J. J. J. Phys. Chem. 1993, 97, 2488.
34. Rovira, M. C.; Novoa, J. J.; Whangbo. M. H.; Williams, J. M. Chem. Phys. 1995, 200, 319.