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Ab initio theoretical predictions of C28, C28H4, C28F4, (TiC28)H4, and MC28 (M=Mg, Al, Si, S, Ca, Sc, Ti, Ge, Zr, and Sn)

J. Chem. Phys. 99, 352 (1993); doi:10.1063/1.465758

Issue Date: 1 July 1993

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Ting Guo, Richard E. Smalley, and Gustavo E. Scuseria
Rice Quantum Institute and Departments of Chemistry and Physics, Rice University, Houston, Texas 77251-1892
Recent experiments have demonstrated that C28 is the smallest fullerene cage that successfully traps elements in its inside. In this work, we have studied the electronic structures, equilibrium geometries, and binding energies of the title molecules at the self-consistent field (SCF) Hartree–Fock level of theory employing basis sets of double-zeta quality. The empty C28 fullerene is found to have a 5A2 open-shell ground state and behaves as a sort of hollow superatom with an effective valence of 4, both toward the outside and inside of the carbon cage. The theoretical evidence suggests that C28H4 and C28F4 should be stable molecules. The possibility of simultaneous bonding from the inside and outside of the C28 shell, as in (TiC28)H4, is also explored. Our calculations show that the binding energy of the MC28 species is a good indicator of the success in experimentally trapping the metal atoms (M) inside the fullerene cage. Based on these results, we propose that elements with electronegativities smaller than 1.54 should form endohedral fullerenes larger than a minimum size which depends on the ionic radius of the trapped atom. This qualitative model, correctly reproduces the available experimental evidence on endohedral fullerenes. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 2 November 1992; accepted 26 March 1993
Permalink: http://link.aip.org/link/?JCPSA6/99/352/1
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KEYWORDS and PACS

Keywords
PACS
  • 36.40.+d
    Studies of special atoms and molecules Atomic and molecular clusters
  • 31.20.Tz
    Electronic structure of atoms and molecules: theory Specific calculations and results Electron correlation and CI calculations
  • YEAR: 1993

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0021-9606 (print)   1089-7690 (online)
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REFERENCES (59)
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  1. H. W. Kroto, J. R. Heath, S. C. O'Brien, R. F. Curl, and R. E. Smalley, Nature 318, 162 (1985).
  2. J. R. Heath, S. C. O'Brien, Q. Zhang, Y. Liu, R. F. Curl, H. W. Kroto, F. K. Tittel, and R. E. Smalley, J. Am. Chem. Soc. 107, 7779 (1985).
  3. E. A. Rohlfing, D. M. Cox, and A. Kaldor, J. Chem. Phys. 81, 3322 (1984).
  4. F. D. Weiss, J. L. Elkind, S. C. O'Brien, R. F. Curl, and R. E. Smalley, J. Am. Chem. Soc. 110, 4464 (1988).
  5. A. Rosen and B. Wastberg, J. Am. Chem. Soc. 110, 8701 (1988).
  6. B. Wastberg and A. Rosen, Phys. Scr. 44, 276 (1991).
  7. P. P. Schmidt, B. I. Dunlap, and C. T. White, J. Phys. Chem. 95, 10 537 (1991).
  8. D. E. Manolopoulos and P. W. Fowler, Chem. Phys. Lett. 187, 1 (1991).
  9. J. Cioslowski and E. D. Fleischman, J. Chem. Phys. 94, 3730 (1991).
  10. J. Cioslowski, J. Am. Chem. Soc. 113, 4139 (1991).
  11. A. H. H. Chang, W. C. Ermler, and R. M. Pitzer, J. Chem. Phys. 94, 5004 (1991).
  12. L. Wang, M. J. Alford, Y. Chai, M. Diener, T. Guo, G. E. Scuseria, and R. E. Smalley, Chem. Phys. Lett. (in press).
  13. Y. Cai, T. Guo, C. Jin, R. E. Haufler, L. P. F. Chibante, J. Fure, L. Wang, J. M. Alford, and R. E. Smalley, J. Phys. Chem. 95, 7568 (1991).
  14. J. H. Weaver, Y. Chai, G. H. Kroll, C. Jin, T. R. Ohno, R. E. Haufler, T. Guo, J. M. Alford, J. Conceicao, L. P. F. Chibante, A. Jain, G. Palmer, and R. E. Smalley, Chem. Phys. Lett. 190, 460 (1992).
  15. M. M. Alvarez, E. G. Gillan, K. Holczer, R. B. Kaner, K. S. Min, and R. L. Whetten, J. Phys. Chem. 95, 10 561 (1991).
  16. C. S. Yannoni, M. Hoinkls, M. S. de Vries, D. S. Bethune, J. R. Salem, M. S. Crowder, and R. D. Johnson, Science 256, 1191 (1992).
  17. H. Shinohara, H. Sato, M. Ohkohohi, Y. Ando, T. Kodama, T. Shida, T. Kato, and Y. Saito, Nature 357, 52 (1992).
  18. R. D. Johnson, M. S. de Vries, J. Salem, D. S. Bethune, and C. S. Yannoni, Nature 355, 239 (1992).
  19. T. Guo, M. Diener, Y. Cai, M. J. Alford, R. E. Haufler, S. M. McClure, T. Ohno, J. H. Weaver, G. E. Scuseria, and R. E. Smalley, Science 257, 1661 (1992).
  20. T. Guo and R. E. Smalley (unpublished results).
  21. J. Almlöf, K. Faegri, Jr., and K. Korsell, J. Comput. Chem. 3, 385 (1982).
  22. M. Häser and R. Ahlrichs, J. Comput. Chem. 10, 104 (1989).
  23. R. Ahlrichs, M. Bar, M. Häser, H. Horn, and C. Kolmel, Chem. Phys. Lett. 162, 165 (1989).
  24. F. B. van Duijneveldt, IBM Research Report RJ945, 1971.
  25. S. Huzinaga, University of Alberta, Technical Report, 1971.
  26. The Ca basis set was taken from the TURBOMOLE library basen.
  27. A. J. H. Wachters, J. Chem. Phys. 52, 1034 (1970).
  28. D. H. Hood, R. M. Pitzer, and H. F. Schaefer, J. Chem. Phys. 71, 705 (1979).
  29. T. H. Dunning, J. Chem. Phys. 66, 1382 (1977).
  30. R. Poirier, R. Kari, and I. Csizmada, Handbook of Gaussian Basis Sets (Elsevier, New York, 1985).
  31. S. Huzinaga, J. Chem. Phys. 42, 1293 (1965),
    32. T. H. Dunning, ibid. 53, 2823 (1970).
  32. S. F. Boys and F. Bernardi, Mol. Phys. 19, 553 (1970).
  33. L. P. Delabroy and G. E. Scuseria (to be published).
  34. H. W. Kroto, Nature 329, 529 (1987).
  35. D. Bakowies and W. Thiel, J. Am. Chem. Soc. 113, 3704 (1991).
  36. M. Feyereisen, M. Gutowski, J. Simons, and J. Almlöf, J. Chem. Phys. 96, 2926 (1992).
  37. B. L. Zhang, C. Z. Wang, K. M. Ho, C. H. Xu, and C. T. Chan, J. Chem. Phys. 97, 5007 (1992).
  38. G. Herzberg, Electronic Spectra and Electronic Structure of Polyatomic Molecules (Van Nostrand Reinhold, New York, 1966).
  39. D. R. Yarkony and H. F. Schaefer III, J. Am. Chem. Soc. 96, 3754 (1974).
  40. P. M. W. Gill, B. G. Johnson, J. A. Pople, and M. A. Frisch, Int. J. Quantum Chem. Symp. 26, 319 (1992).
  41. A. D. Becke, Phys. Rev. A 38, 3098 (1988).
  42. C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988).
  43. G. E. Scuseria, J. Chem. Phys. 97, 7528 (1992).
  44. P. M. W. Gill, B. G. Johnson, J. A. Pople, and M. A. Frisch, Chem. Phys. Lett. 197, 499 (1992).
  45. C. Elschenbroich and A. Salzer, Organometallics (VCH, New York, 1988), Chap. 15; P. Powell, Principles of Organometallic Chemistry, 2nd ed. (Chapman and Hall, New York, 1988), p. 402.
  46. B. I. Dunlap, O. D. Häberlen, and N. Rosch, J. Phys. Chem. 96, 9095 (1992).
  47. O. D. Häberlen, N. Rösch, and B. I. Dunlap, Chem. Phys. Lett. 200, 418 (1992).
  48. F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, 5th ed. (Wiley, New York, 1988).
  49. A. H. H. Chang and R. M. Pitzer, J. Am. Chem. Soc. 111, 2500 (1988).
  50. M. M. Ross, H. H. Nelson, J. H. Callahan, and S. W. McElvany, J. Phys. Chem. 96, 5231 (1992).
  51. L. Pauling, The Nature of the Chemical Bond and the Structure of Molecules and Crystals (Cornell University, Ithaca, 1939).
  52. J. Emsley, The Elements (Clarendon, Oxford, 1991);
    53. see also Periodic Table of the Elements (Sargent Welch Scientific, New York, 1980).
  53. K, Cs, Ref. 4; Ca, Ref. 12; Sc, La, Y, Refs. 13–17; Ti, Zr, Hf, U, Ref. 19; Ba, Sr, Ref. 54; rare earths, Ref. 55; Na, R. E. Smalley (unpublished results).
  54. R. E. Smalley, in Atomic and Molecular Clusters, edited by E. R. Bernstein (Elsevier, New York, 1990), Chap. 1.
  55. E. G. Gillan, C. Yeretzian, K. S. Min, M. M. Alvarez, R. L. Whetten, and R. B. Kaner, J. Phys. Chem. 96, 6869 (1992).
  56. T. Pradeep, G. U. Kulkarni, K. R. Kannan, T. N. Guru Row, and C. N. R. Rao, J. Am. Chem. Soc. 114, 2272 (1992).
  57. T. Weiske, T. Wong, W. Kratschmer, J. K. Terlouw, and H. Schwarz, Angew. Chem. Int. Ed. Engl. 31, 183 (1992).
  58. Z. Wan, F. F. Christian, and S. L. Anderson (preprint).
  59. R. E. Smalley, Acc. Chem. Res. 25, 98 (1992).

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