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Chemical reactions of silicon clusters

J. Chem. Phys. 101, 8108 (1994); doi:10.1063/1.468238

Issue Date: 1 November 1994

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Mushti V. Ramakrishna and Jun Pan
The Department of Chemistry, New York University, New York, New York 10003-6621
Smalley and co-workers discovered that chemisorption reactivities of silicon clusters vary over three orders of magnitude as a function of cluster size. In particular, they found that Si33, Si39, and Si45 clusters are least reactive towards various reagents compared to their immediate neighbors in size. We explain these observations based on our stuffed fullerene model. This structural model consists of bulk-like core of five atoms surrounded by fullerene-like surface. Reconstruction of the ideal fullerene geometry gives rise to fourfold coordinated crown atoms and pi-bonded dimer pairs. This model yields unique structures for Si33, Si39, and Si45 clusters without any dangling bonds and thus explains their lowest reactivity towards chemisorption of closed shell reagents. This model is also consistent with the experimental finding of Jarrold and Constant that silicon clusters undergo a transition from prolate to spherical shapes at Si27. We justify our model based on an in depth analysis of the differences between carbon and silicon chemistry and bonding characteristics. Using our model, we further explain why dissociative chemisorption occurs on bulk surfaces while molecular chemisorption occurs on cluster surfaces. We also explain reagent specific chemisorption reactivities observed experimentally based on the electronic structures of the reagents. Finally, experiments on SixXy (X = B, Al, Ga, P, As, AlP, GaAs) are suggested as a means of verifying the proposed model. We predict that Six(AlP)y and Six(GaAs)y (x=25,31,37;y=4) clusters will be highly inert and it may be possible to prepare macroscopic samples of these alloy clusters through high temperature reactions. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 23 May 1994; accepted 28 July 1994
Permalink: http://link.aip.org/link/?JCPSA6/101/8108/1
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KEYWORDS and PACS

Keywords
PACS
  • 82.65.My
    Physical chemistry Surface and interface chemistry Chemisorption
  • 36.40.+d
    Studies of special atoms and molecules Atomic and molecular clusters
  • 82.65.Yh
    Physical chemistry Surface and interface chemistry Other surface and interface chemical processes
  • YEAR: 1994

PUBLICATION DATA

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

REFERENCES (49)
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  1. J. L. Elkind, J. M. Alford, F. D. Weiss, R. T. Laaksonen, and R. E. Smalley, J. Chem. Phys. 87, 2397 (1987);
    2. S. Maruyama, L. R. Anderson, and R. E. Smalley, ibid. 93, 5349 (1990);
    J. M. Alford, R. T. Laaksonen, and R. E. Smalley, ibid. 94, 2618 (1991);
    L. R. Anderson, S. Maruyama, and R. E. Smalley, Chem. Phys. Lett. 176, 348 (1991).
  2. J. C. Phillips, J. Chem. Phys. 88, 2090 (1988).
  3. D. A. Jelski, Z. C. Wu, and T. F. George, Chem. Phys. Lett. 150, 447 (1988).
  4. E. Kaxiras, Chem. Phys. Lett. 163, 323 (1989);
    5. Phys. Rev. Lett. 64, 551 (1990).
  5. C. H. Patterson and R. P. Messmer, Phys. Rev. B 42, 7530 (1990).
  6. B. L. Swift, D. A. Jelski, D. S. Higgs, T. T. Rantala, and T. F. George, Phys. Rev. Lett. 66, 2686 (1991);
    7. D. A. Jelski, B. L. Swift, T. T. Rantala, X. Xia, and T. F. George, J. Chem. Phys. 95, 8552 (1991).
  7. U. Röthlisberger, W. Andreoni, and M. Parrinello, Phys. Rev. Lett. 72, 665 (1994).
  8. M. F. Jarrold and V. A. Constant, Phys. Rev. Lett. 67, 2994 (1991).
  9. D. W. Brenner, B. I. Dunlap, J. A. Harrison, J. W. Mintmire, R. C. Mowrey, D. H. Robertson, and C. T. White, Phys. Rev. B 44, 3479 (1991).
  10. R. F. Curl and R. E. Smalley, Sci. Am. 10, 54 (1991).
  11. W. O. J. Boo, J. Chem. Ed. 69, 605 (1992).
  12. P. W. Fowler, in FULLERENES: Status and Perspectives, edited by C. Taliani, G. Ruani, and R. Zamboni (World Scientific, Singapore, 1992).
  13. M. Menon and K. R. Subbaswamy, Chem. Phys. Lett. 219, 219 (1994).
  14. M. L. Cohen and S. G. Louie, Annu. Rev. Phys. Chem. 35, 537 (1984).
  15. M. Lannoo and P. Friedel, Atomic and Electronic Structure of Surfaces (Springer-Verlag, Berlin, 1991), Chap. 4.
  16. J. E. Northrup and M. L. Cohen, Phys. Rev. Lett. 49, 1349 (1982).
  17. D. J. Chadi, Phys. Rev. Lett. 43, 43 (1979).
  18. C. M. Lieber, Chem. Eng. News 72(16), 28 (1994).
  19. R. Wolkow and Ph. Avouris, Phys. Rev. Lett. 60, 1049 (1988);
    20. Ph. Avouris and R. Wolkow, Phys. Rev. B 39, 5091 (1989);
    Ph. Avouris, J. Phys. Chem. 94, 2246 (1990).
  20. Foundation Set for General and Organic Chemistry (Jones and Bartlett, Boston, 1994).
  21. E. Kaxiras and K. C. Pandey, Phys. Rev. B 38, 12736 (1988).
  22. K. Raghavachari and V. Logovinsky, Phys. Rev. Lett. 55, 2853 (1985);
    23. K. Raghavachari, J. Chem. Phys. 83, 3520 (1985);
    84, 5672 (1986);
    K. Raghavachari and C. M. Rohlfing, Chem. Phys. Lett. 143, 428 (1988);
    J. Chem. Phys. 89, 2219 (1989);
    C. M. Rohlfing and K. Raghavachari, Chem. Phys. Lett. 167, 559 (1990);
    K. Raghavachari and C. M. Rohlfing, J. Chem. Phys. 94, 3670 (1991).
  23. F. Stillinger and T. Weber, Phys. Rev. B 31, 5262 (1985).
  24. R. Biswas and D. R. Hamann, Phys. Rev. Lett. 55, 2001 (1985);
    25. Phys. Rev. B 36, 6434 (1987).
  25. J. Tersoff, Phys. Rev. Lett. 56, 632 (1986);
    26. P. C. Kelires and J. Tersoff, ibid. 61, 562 (1988).
  26. J. R. Chelikowsky, J. C. Phillips, M. Kamal, and M. Strauss, Phys. Rev. Lett. 62, 292 (1989);
    27. J. R. Chelikowsky, K. M. Glassford, and J. C. Phillips, Phys. Rev. B 44, 1538 (1991).
  27. B. C. Bolding and H. C. Andersen, Phys. Rev. B 41, 10568 (1990).
  28. M. L. Cohen and W. D. Knight, Phys. Today 43(12), 42 (1990).
  29. Semiconductors, edited by O. Madelung (Springer-Verlag, Berlin, 1991).
  30. M. T. Yin and M. L. Cohen, Phys. Rev. Lett. 50, 2006 (1983);
    31. Phys. Rev. B 29, 6996 (1983).
  31. B. B. Pate, Surf. Sci. 83, 165 (1986).
  32. J. Bokor, R. Storz, R. R. Freeman, and P. H. Bucksbaum, Phys. Rev. Lett. 57, 881 (1986).
  33. K. Raghavachari and J. S. Binkley, J. Chem. Phys. 87, 2191 (1987).
  34. W. Andreoni, D. Scharf, and P. Giannozzi, Chem. Phys. Lett. 173, 449 (1990).
  35. V. Parasuk and J. Almlöf, J. Chem. Phys. 94, 8172 (1991).
  36. M. Menon, K. R. Subbaswamy, and M. Sawtarie, Phys. Rev. B 48, 8398 (1993).
  37. M. T. Yin and M. L. Cohen, Phys. Rev. B 26, 5668 (1982).
  38. D. Tománek and M. Schlüter, Phys. Rev. Lett. 56, 1055 (1986);
    39. Phys. Rev. B 36, 1208 (1987);
    Phys. Rev. Lett. 67, 2331 (1991).
  39. M. Menon and K. R. Subbaswamy, Phys. Rev. B 47, 12754 (1993).
  40. M. F. Jarrold, J. E. Bower, and K. M. Creegan, J. Chem. Phys. 90, 3615 (1989);
    41. K. M. Creegan and M. F. Jarrold, J. Am. Chem. Soc. 112, 3768 (1990);
    M. F. Jarrold, U. Ray, and K. M. Creegan, J. Chem. Phys. 93, 224 (1990);
    U. Ray and M. F. Jarrold, ibid. 94, 2631 (1991).
  41. L. Kubler, E. K. Hill, D. Bolmont, and G. Gewinner, Surf. Sci. 183, 503 (1987).
  42. S. Tanaka, M. Onchi, and M. Nishijima, Surf. Sci. 191, L756 (1987).
  43. F. Bozso and Ph. Avouris, Phys. Rev. B 38, 3943 (1988).
  44. K. Takayanagi, Y. Tanishiro, M. Takahashi, and S. Takahashi, J. Vac. Sci. Technol. A 3, 1502 (1985).
  45. K. C. Pandey, Phys. Rev. Lett. 47, 1913 (1981);
    46. Phys. Rev. B 25, 4338 (1982).
  46. J. L. Feldman, E. Kaxiras, and X.-P. Li, Phys. Rev. B 44, 8334 (1991).
  47. G. Herzberg, Molecular Spectra and Molecular Structure I. Spectra of Diatomic Molecules (Van Nostrand, New York, 1950), p. 343.
  48. M. A. Al-Laham, G. W. Trucks, and K. Raghavachari, J. Chem. Phys. 96, 1137 (1992).
  49. R. W. Siegel, Phys. Today 46(10), 64 (1993).

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