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On the kinetics of the Al13−+Cl2 reaction: Cluster degradation in consecutive steps

J. Chem. Phys. 131, 174304 (2009); doi:10.1063/1.3257684

Published 2 November 2009 | See: Publisher's Note

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Matthias Olzmann,1 Ralf Burgert,2 and Hansgeorg Schnöckel2
1Institut für Physikalische Chemie, Karlsruher Institut für Technologie (KIT), Kaiserstr. 12, 76131 Karlsruhe, Germany
2Institut für Anorganische Chemie, Karlsruher Institut für Technologie (KIT), Kaiserstr. 12, 76131 Karlsruhe, Germany
The kinetics of the reaction system initiated by the Al13−+Cl2 reaction was experimentally studied in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The Al13− clusters were produced by laser desorption/ionization of LiAlH4, then transferred into the ICR cell, cooled by collisions with Ar, and exposed to an excess of Cl2 with a concentration of ~108  cm−3. Relative concentration-time profiles of Aln− clusters with n=13, 11, 9, and 7 as well as profiles of Cl− ions have been recorded. Other ionic species, besides traces of Al12Cl−, were not found, which indicates a double-step degradation mechanism via the odd-numbered Aln− clusters. From a kinetic analysis of the experimental results, a rate coefficient of (5±2)×10−10  cm3 s−1 for the Al13−+Cl2 reaction was obtained. Furthermore, it is inferred from a simultaneous fit of all concentration-time profiles that the Aln−+Cl2 reactions for n=13, 11, 9, and 7 occur with rate coefficients near the Langevin limit in the range kbim~(5±4)×10−10  cm3 s−1. The branching ratios between the Aln−2−-producing and Cl−-producing channels of a given cluster AlnCl2− indicate an increasing contribution of the Cl−-producing channels with decreasing cluster size. Statistical rate theory calculations on the basis of molecular data from quantum chemical calculations show that the experimental Aln− profiles are compatible with a sequence of association-elimination reactions proceeding via the formation of highly excited AlnCl2− adducts followed by a sequential elimination of two AlCl molecules. Rate coefficients for these reactions were calculated, and the production of Cl− was shown probably not to proceed via these AlnCl2− intermediates. ©2009 American Institute of Physics
History: Received 3 July 2009; accepted 9 October 2009; published 2 November 2009; publisher error corrected 4 November 2009
Permalink: http://link.aip.org/link/?JCPSA6/131/174304/1
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ERRATUM

  1. Publisher's Note: “On the kinetics of the Al13−+Cl2 reaction: Cluster degradation in consecutive steps” [J. Chem. Phys. 131, 174304 (2009)]
    Matthias Olzmann et al.
    J. Chem. Phys. 131, 199902 (2009)

EPAPS

KEYWORDS and PACS

Keywords
PACS
  • 82.30.Cf
    Atom and radical chemical reactions; chain reactions, molecule-molecule reactions
  • 82.30.Nr
    Association, addition, insertion, cluster formation (chemical reactions)
  • 36.40.-c
    Atomic and molecular clusters
  • 82.20.Pm
    Chemical rate constants, reaction cross sections, and activation energies
  • 82.20.Db
    Transition state theory and statistical theories of rate constants (chemical kinetics)
  • YEAR: 2009

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (51)
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For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. A. W. Castleman and K. H. Bowen, J. Phys. Chem. 100, 12911 (1996).
  2. M. B. Knickelbein, Annu. Rev. Phys. Chem. 50, 79 (1999).
  3. R. Burgert and H. Schnöckel, Chem. Commun. (Cambridge) 2008, 2075.
  4. B. K. Rao and P. Jena, J. Chem. Phys. 111, 1890 (1999).
  5. R. Fournier, J. Chem. Theory Comput. 3, 921 (2007).
  6. R. Burgert, H. Schnöckel, A. Grubisic, X. Li, S. T. Stokes, K. H. Bowen, G. F. Ganteför, B. Kiran, and P. Jena, Science 319, 438 (2008).
  7. D. E. Bergeron, A. W. Castleman, Jr., T. Morisato, and S. N. Khanna, J. Chem. Phys. 121, 10456 (2004).
  8. D. E. Bergeron, A. W. Castleman, Jr., T. Morisato, and S. H. Khanna, Science 304, 84 (2004).
  9. D. E. Bergeron, P. J. Roach, A. W. Castleman, Jr., N. O. Jones, and S. N. Khanna, Science 307, 231 (2005).
  10. N. O. Jones, J. U. Reveles, S. N. Khanna, D. E. Bergeron, P. J. Roach, and A. W. Castlemann, Jr., J. Chem. Phys. 124, 154311 (2006).
  11. Y. -K. Han and J. Jung, J. Chem. Phys. 125, 084101 (2006).
  12. Y. -K. Han and J. Jung, J. Am. Chem. Soc. 130, 2 (2008).
  13. R. Burgert, H. Schnöckel, M. Olzmann, and K. H. Bowen, Jr., Angew. Chem., Int. Ed. 45, 1476 (2006).
  14. R. Burgert, S. T. Stokes, K. H. Bowen, and H. Schnöckel, J. Am. Chem. Soc. 128, 7904 (2006).
  15. A. G. Marshall, C. L. Hendrickson, and G. S. Jackson, Mass Spectrom. Rev. 17, 1 (1998).
  16. A. G. Marshall, T. C. L. Wang, and T. L. Ricca, J. Am. Chem. Soc. 107, 7893 (1985).
  17. S. Guan and A. G. Marshall, Int. J. Mass Spectrom. Ion Process. 157/158, 5 (1996).
  18. See EPAPS supplementary material http://dx.doi.org/10.1063/1.3257684 for numerical values of relative concentration-time profiles and calculated molecular data. [EPAPS]
  19. M. B. Comisarow, J. Chem. Phys. 69, 4097 (1978).
  20. P. A. Limbach, P. B. Grosshans, and A. G. Marshall, Anal. Chem. 65, 135 (1993).
  21. R. G. Parr and W. Yang, Density-Functional Theory of Atoms and Molecules (Oxford University Press, Oxford, 1989).
  22. R. Ahlrichs and S. D. Elliott, Phys. Chem. Chem. Phys. 1, 13 (1999).
  23. J. B. Perdew, Phys. Rev. B 33, 8822 (1986).
  24. A. D. Becke, Phys. Rev. A 38, 3098 (1988).
  25. A. Schäfer, H. Horn, and R. Ahlrichs, J. Chem. Phys. 97, 2571 (1992).
  26. K. Eichkorn, O. Treutler, H. Öhm, M. Häser, and R. Ahlrichs, Chem. Phys. Lett. 240, 283 (1995).
  27. K. Eichkorn, F. Weigend, O. Treutler, and R. Ahlrichs, Theor. Chem. Acc. 97, 119 (1997).
  28. R. Ahlrichs, M. Bär, M. Häser, H. Horn, and C. Kölmel, Chem. Phys. Lett. 162, 165 (1989).
  29. E. E. Nikitin, Teor. Eksp. Khim. 1, 144 (1965).
  30. P. Pechukas and J. C. Light, J. Chem. Phys. 42, 3281 (1965).
  31. W. Chesnavich and M. T. Bowers, in Gas Phase Ion Chemistry, edited by M. T. Bowers (Academic, New York, 1979), Vol. 1, p. 119.
  32. R. G. Gilbert and S. C. Smith, Theory of Unimolecular and Recombination Reactions (Blackwell, Oxford, 1990).
  33. T. Baer and W. L. Hase, Unimolecular Reaction Dynamics (Oxford University Press, Oxford, 1996).
  34. G. H. Peslherbe and W. L. Hase, J. Chem. Phys. 105, 7432 (1996).
  35. R. A. Marcus and O. K. Rice, J. Phys. Colloid Chem. 55, 894 (1951).
  36. R. A. Marcus, J. Chem. Phys. 20, 359 (1952).
  37. L. Brouwer, C. J. Cobos, J. Troe, H. -R. Dübal, and F. F. Crim, J. Chem. Phys. 86, 6171 (1987).
  38. J. Troe, J. Chem. Phys. 75, 226 (1981).
  39. T. Beyer and D. F. Swinehart, Commun. ACM 16, 379 (1973).
  40. J. Troe, J. Chem. Phys. 79, 6017 (1983).
  41. M. Olzmann and J. Troe, Ber. Bunsenges. Phys. Chem. 96, 1227 (1992).
  42. D. Schröder and H. Schwarz, Angew. Chem., Int. Ed. Engl. 29, 1431 (1990).
  43. S. Le Caër, M. Heninger, P. Pernot, and H. Mestdagh, Phys. Chem. Chem. Phys. 4, 1855 (2002).
  44. P. Langevin, Ann. Chim. Phys. 5, 245 (1905).
  45. J. I. Steinfeld, J. S. Francisco, and W. L. Hase, Chemical Kinetics and Dynamics (Prentice-Hall, Englewood Cliffs, 1989).
  46. CRC Handbook of Chemistry and Physics, 75th ed., edited by D. R. Lide (CRC, Boca Raton, 1994).
  47. MATHCAD 2000 PROFESSIONAL, MathSoft Inc., 1986–1999.
  48. M. Olzmann, Ber. Bunsenges. Phys. Chem 101, 533 (1997).
  49. P. W. Atkins, Molecular Quantum Mechanics, 2nd ed. (Oxford University Press, Oxford, 1983).
  50. J. Schwarz, D. Schröder, H. Schwarz, C. Heinemann, and J. Hrušák, Helv. Chim. Acta 79, 1110 (1996).
  51. X. Li, H. Wu, X. Wang, and L. Wang, Phys. Rev. Lett. 81, 1909 (1998).

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