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The results of CI(SD) calculations performed with BIGGMOLI-NONAME presented.(AIP)

Coordination chemistry of metal surfaces: Chemisorption of PF3

J. Chem. Phys. 74, 5911 (1981); doi:10.1063/1.440909

Issue Date: 15 May 1981

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F. Nitschké, G. Ertl, and J. Küppers
Institut für Physikalische Chemie, Universität München, München, West Germany
The electronic and thermal properties of PF3 bonded to surfaces of Cr, Fe, Ni, Cu, Ru, Pd, Ir, and Pt were investigated by means of ultraviolet photoelectron spectroscopy (UPS), electron energy loss sectroscopy, LEED, and thermal desorption. Bond formation can be described in terms of coupling of the highest occupied ligand orbital (sigma-donor 8a1) to metallic s states and of ''back donation'' of metallic d electrons into the lowest empty ligand orbital (pi-acceptor 7e). The observed lowering of the ionization potential of the 8a1 level exhibits close similarities with the properties of the corresponding zero-valent mononuclear complex compounds, indicating that in this case the chemisorption bond has to be considered as an essentially local phenomenon. The agreement is best with the fcc metals Ni, Pd, Ir, and Pt, whereas larger variations (as well as a dependence on the crystallographic orientation of the surface) were found with the bcc metals Cr and Fe. Ordered 2×2 overlayers observed with Ni(111) and Pd(111) surfaces are interpreted in terms of a simple structure model based on the van der Waals diameter of PF3 and on linear bond formation. Thermal desorption takes place at temperatures which are very close to those observed for CO, indicating very similar bond strengths for both ligands. Thermal decomposition of PF3 (which obviously needs several metal atoms and is therefore not observed with mononuclear complexes) was found to dominate with Cr and Fe surfaces. Although the sigma-donor coupling is rather pronounced with the system PF3Cu(110) in this case thermal desorption already takes place around 200 K. This low thermal stability is presumably the reason why so far no mononuclear Cu–PF3 complex could be prepared. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
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KEYWORDS and PACS

Keywords
PACS
  • 82.65.My
    Physical chemistry Surface processes Sorption and accommodation coefficients
  • YEAR: 1981

PUBLICATION DATA

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

REFERENCES (38)
View in Separate Window/Tab
  1. For a recent review, see, for example, E. L. Muetterties, T. N. Rhodin, E. Band, C. F. Brucker, and W. R. Pretzer, Chem. Rev. 79, 91 (1979). [ISI] [ChemPort]
  2. See, for example, R. P. Messmer, in The Nature of the Surface Chemical Bond, edited by T. N. Rhodin and G. Ertl (North-Holland, Amsterdam, 1979).
  3. E. W. Plummer, W. R. Salaneek, and J. S. Miller, Phys. Rev. B 18, 1673 (1978). [Inspec]
  4. Th. Kruck, Angew. Chem. 79, 27 (1967).
  5. R. A. Head, J. F. Nixon, G. J. Sharp, and R. J. Clark, J. Chem. Soc. Dalton Trans. 3, 2054 (1975).
  6. R. A. Head, J. F. Nixon, N. P. C. Westwood, and R. J. Clark, J. Organomet. Chem. 145, 75 (1978). [ChemPort]
  7. J. Chatt and G. J. Leigh, Angew. Chem. 90, 442 (1978). [ChemPort]
  8. D. L. S. Brown, J. A. Connor, and H. A. Skinner, J. Chem. Soc. Faraday Trans. 1 70, 1649 (1974). [ChemPort]
  9. G. Blyholder and R. Sheets, J. Colloid Interface Sci. 46, 380 (1974). [Inspec]
  10. J. Kuppers and H. Michel, Appl. Surf. Sci. 3, 179 (1978). [Inspec]
  11. H. Conrad, G. Ertl, J. Kuppers, and E. E. Latta, Faraday Discuss. Chem. Soc. 58, 116 (1974). [ISI]
  12. J. P. Maier and D. W. Turner, J. Chem. Soc. Faraday Trans. 2 68, 711 (1972). [ISI] [ChemPort]
  13. P. J. Bassett and D. R. Lloyd, J. Chem. Soc. Dalton Trans. 1, 248 (1972).
  14. H. D. Hagstrum, Surf. Sci. 54, 197 (1976). [Inspec]
  15. J. Q. Broughton and D. L. Perry, Surf. Sci. 74, 307 (1978). [Inspec] [ChemPort]
  16. B. I. Dunlap and J. W. Gadzuk, Surf. Sci. 94, 89 (1980). [Inspec]
  17. R. Hesse, P. Staib, and D. Menzel, Appl. Phys. 18, 227 (1979).
  18. C. Malatesta and S. Cenini, Zero-valent Compounds of Metals, (Academic, New York, 1974), p. 97.
  19. Handbook of Chemistry and Physics, 55th ed. (Chemical Rubber, Cleveland, 1974).
  20. I. H. Hillier and V. R. Saunders, Chem. Comm. 1, 316 (1970).
  21. P. J. Bassett, D. R. Lloyd, I. H. Hillier, and V. R. Saunders, Chem. Phys. Lett. 6, 253 (1970). [Inspec]
  22. H. Itoh and B. Kunz, Chem. Phys. Lett. 64, 576 (1979). [Inspec]
  23. P. J. Bassett and D. R. Lloyd, J. Chem. Soc. Dalton Trans. 1, 248 (1972).
  24. G. Doyen and G. Ertl, “Proceedings of the 7th International Vacuum Congress,” Vienna (1977), p. 703.
  25. G. Doyen and G. Ertl, Surf. Sci. 69, 157 (1977). [Inspec] [ISI] [ChemPort]
  26. K. Klapper, H. F. Kempin, and G. Ertl, Phys. Rev. Lett. 41, 333 (1978).
  27. D. R. Lloyd and E. W. Schlag, Inorg. Chem. 8, 2544 (1969). [ISI] [ChemPort]
  28. G. Broden, T. N. Rhodin, C. Brucker, R. Benbow, and Z. Hurych, Surf. Sci. 59, 593 (1976).
  29. J. H. Darling and J. S. Ogden, Inorg. Chem. 11, 666 (1972); [ISI] [ChemPort]
    30. H. Huber, P. Kündig, M. Moskovits and G. A. Ozin, Nature (London) Phys. Sci. 235, 98 (1972).
  30. J. A. Connor, Topics in Current Chemistry (Springer, Berlin, 1977), Vol. 71, p. 71.
  31. M. Moskovits and G. A. Ozin, Cryochemistry (Wiley, New York, 1976).
  32. J. E. Hulse and M. Moskovits, Surf. Sci. 57, 125 (1976); [Inspec] [ChemPort]
    33. 61, 302 (1976). [Inspec]
  33. K. Christmann, O. Schober, and G. Ertl, J. Chem. Phys. 60, 4719 (1974). [ISI]
  34. H. Conrad, G. Ertl, J. Küppers, and E. E. Latta, Solid State Commun. 17, 613 (1975). [Inspec]
  35. H. Itoh and B. Kunz, “Proceedings of the Symposium on Homogeneous Catalysis,” Corpus Christi, Texas (Nov. 1978).
  36. S. Fraga, J. Karwowski, and K. M. S. Saxena, Handbook of Atomic Data (Elsevier, Amsterdam, 1976);
    37. G. J. Ballhausen and H. B. Gray, Molecular Orbital Theory (Benjamin, New York, 1965), p. 120.
  37. H. L. Yu, J. Chem. Phys. 69, 1755 (1978). [ISI] [ChemPort]
  38. S. Anderson and J. B. Pendry, Phys. Rev. Lett. 43, 363 (1979). [ISI] [ChemPort]

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