Theoretical investigations of reactions between AlH(¹Σ) and XνH (X=Cl, OH)

Abstract

Reaction paths of AlH(¹Σ) with X–H (X=Cl, OH) are characterized by the HF/6-31G(d), MP2(fc)/6-31G(d) and MP2(full)/6-31G(d) levels, respectively; energies of reactions and barriers are calculated by the G2 level of theory and MP4SDQ/6-31G(d)//MP2(fc)/6-31G(d). The calculations show that there are two parallel reaction channels: one is an addition reaction to give H₂AlX via the three-membered ring transition state (TS); the other is a dehydrogenation reaction to give (AlX+H₂) via the four-membered ring TS. General statistical thermodynamics (GST) and Eyring transition state theory (TST) with Wigner correction are also used to compute the thermodynamic functions, equilibrium constants, A factors, and rate constants of these reaction channels at 100–1100 K. The results show that the unique product (AlX+H₂) is to be obtained.

References

1. J. E. Butler, J. W. Heming, L. P. Goss and M. C. Lin, Chem. Phys., 1981, 56, 355.
2. D. A. Lichtin, M. R. Berman and M. C. Lin, Chem. Phys. Lett., 1984, 108, 18.
3. M. R. Berman and M. C. Lin, J. Chem. Phys., 1984, 81, 5743.
4. J. A. Harrison and R. G. A. R. Maclagan, Chem. Phys. Lett., 1988, 146, 243.
5. J. A. Harrison, R. F. Meads and L. F. Phillips, Chem. Phys. Lett., 1988, 150, 299.
6. J. K. Rice, N. J. Caldwell and H. H. Nelson, J. Phys. Chem., 1989, 93, 3600.
7. M. Markus, P. Roth and T. Just, Int. J. Chem. Kinet., 1996, 28, 171.
8. N. L. Garland, C. T. Stanton, J. W. Fleming, A. P. Baronavski and H. H. Nelson, J. Phys. Chem., 1990, 94, 4952.
9. M. H. Begemann, R. W. Dreyfus and J. M. Jasinski, Chem. Phys. Lett., 1989, 155, 351.
10. M. Nemoto, A. Suzuki, H. Nakamura, K. Shibuya and K. Obi, Chem. Phys. Lett., 1989, 162, 467.
11. M. S. Gordon, Y. Xie, Y. Yamaguchi, R. S. Grev and H. F. Schaefer III, J. Am. Chem. Soc., 1993, 115, 1503.
12. J. M. Jasinski, R. Becerra and R. Walsh, Chem. Rev., 1995, 95, 1203.
13. S. H. Bauer, Chem. Rev., 1996, 96, 1907.
14. H. B. Schlegel, A. G. Baboul and S. J. Harris, J. Phys. Chem., 1996, 100, 9774.
15. E. Hwang and P. J. Dagdigian, J. Chem. Phys., 1995, 102, 2426.
16. M. Yang, S. Gregurick, M. H. Alexander and P. J. Dagdigian, J. Chem. Phys., 1995, 102, 2413.
17. J. M. Parnis and G. A. Ozin, J. Phys. Chem., 1989, 93, 1215.
18. J. M. Parnis and G. A. Ozin, J. Phys. Chem., 1989, 93, 1220.
19. G. V. Chertihin and L. Andrews, J. Phys. Chem., 1993, 97, 10295.
20. W.-H. Fang, Chem. Phys. Lett., 1996, 260, 565.
21. E. R. Davidson, Isr. J. Chem., 1993, 33, 243.
22. G. Z. Ju and W. Liu, J. Mol. Sci. (Beijing), 1993, 9, 129.
23. Gaussian-92/DFT, Revision F.2, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. W. Wong, J. B. Foresman, M. A. Robb, M. Head-Gordon, E. S. Replogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L. Martin, D. J. Fox, D. J. Defrees, J. Baker, J. P. Stewart and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1993.
24. Gaussian-94, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, G. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1995.
25. J. Baker, J. Comput. Chem., 1986, 7, 385.
26. J. Baker, J. Comput. Chem., 1987, 8, 563.
27. H. B. Schlegel, J. Comput. Chem., 1982, 3, 214.
28. L. A. Curtiss, K. Raghavachari, G. W. Trucks and J. A. Pople, J. Chem. Phys., 1991, 94, 7221.
29. C. Gonzalez and H. B. Schlegel, J. Chem. Phys., 1989, 90, 2154.
30. C. Gonzalez and H. B. Schlegel, J. Phys. Chem., 1990, 94, 5523.
31. T. L. Hill, Statistical Thermodynamics, Addison-Wesley, New York, 1960.
32. G.-Z. Ju, W.-Y. Ma and K. Christoffel, Int. J. Quantum Chem., 1988, S22, 343.
33. A. P. Scott and L. Radom, J. Phys. Chem., 1996, 100, 16 502.