Theoretica chimica acta

, Volume 74, Issue 6, pp 479–491

The atomic states of nickel

  • Charles W. BauschlicherJr
  • Per Siegbahn
  • Lars G. M. Pettersson
Article

Abstract

The Ni 3d9 4s1(3D)−3d10(1S) and 3d9 4s1(3D)-3d84s2(3F) atomic excitation energies have been computed using large multireference CI wave functions in conjunction with a large ANO basis set. Radial correlation effects in the 3d shell are found to be very important and are included using CASSCF wave functions having the 3d and correlating 3d′ orbitals in the active space. The previous discrepancy (0.5 eV) with experiment for the 3D1S excitation is reduced to 0.1 eV when the 3d→3d′ references are included in the CI. For the 3F state, the 4s-4p near degeneracy gives rise to important 4s2→4p2 excitations in addition to the 3d→3d′ excitations which are important for the 3D and 1S states. Inclusion of only 3d-3d′ correlation in the 3F and 3D CI reference spaces yields a 3F3D separation which is in error by 0.12 eV. Addition of the 4s2→4p2 excitations to the 3F reference space is estimated to increase the discrepancy with experiment by an additional 0.1 eV.

Key words

Ni atom Correlation energy Atomic separations 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Martin RL (1980) Chem Phys Lett 75:290Google Scholar
  2. 2.
    Dunning TH, Botch BH, Harrison JF (1980) J Chem Phys 72:3419Google Scholar
  3. 3.
    Botch BH, Dunning TH, Harrison JF (1981) J Chem Phys 75:3466Google Scholar
  4. 4.
    Bauschlicher CW, Walch SP, Partridge H (1982) J Chem Phys 76:1033Google Scholar
  5. 5.
    Werner HJ (1984) Faraday Symp Chem Soc 19:202Google Scholar
  6. 6.
    Rohlfing CM, Martin RL (1985) Chem Phys Lett 115:104Google Scholar
  7. 7. (a)
    Salter EA, Adamowicz L, Bartlett RJ (1985) Chem Phys Lett 122:23; also see erratum,Google Scholar
  8. 7. (b)
    Salter EA, Adamowicz L, Bartlett RJ (1986) Chem Phys Lett 130:152Google Scholar
  9. 8.
    Langhoff SR, Bauschlicher CW (1986) J Chem Phys 84:4485Google Scholar
  10. 9.
    Moore CE (1949) Atomic energy levels. Natl Bur Stand (US) 467Google Scholar
  11. 10.
    Martin RL, Hay PJ (1981) J Chem Phys 75:4539Google Scholar
  12. 11.
    Walch SP, Bauschlicher CW, Langhoff SR (1985) J Chem Phys 83:5351Google Scholar
  13. 12.
    Gray JA, Rice SF, Field RW (1985) J Chem Phys 82:4717Google Scholar
  14. 13.
    Langhoff SR, Davidson ER (1974) Int J Quantum Chem 8:61; Davidson ER (1984) In: Daudel R, Pullman B (eds) The world of quantum chemistry. Reidel, DordrechtGoogle Scholar
  15. 14.
    Rohlfing CM (1986) Chem Phys Lett 127:183Google Scholar
  16. 15.
    Froese-Fischer C (1977) J Phys B10:1241Google Scholar
  17. 16.
    Partridge H, to be publishedGoogle Scholar
  18. 17.
    Raffenetti RC (1973) J Chem Phys 58:4452Google Scholar
  19. 18.
    Almlöf J, Taylor PR (1987) J Chem Phys 86:4070Google Scholar
  20. 19.
    Hay PJ (1977) J Chem Phys 66:4377Google Scholar
  21. 20.
    Chong DP, Langhoff SR (1986) J Chem Phys 84:5606. The direct-CI MCPF program was written by Blomberg MRA, Siegbahn PGoogle Scholar
  22. 21.
    Siegbahn PEM, Heiberg A, Roos BO, Levy B (1980) Physica Scripta 21:323; Roos BO, Taylor PR, Siegbahn PEM (1980) Chem Phys 48:157; Siegbahn PEM, Almlöf J, Heiberg A, Roos BO (1981) J Chem Phys 74:2381Google Scholar
  23. 22.
    Dunning TH (1984) In: Dykstra CE (ed) Advanced theories and computational approaches to the electronic structure of molecules. Reidel, DordrechtGoogle Scholar
  24. 23.
    Bauschlicher CW, Taylor PR (1988) Theor Chim Acta 74:63–73Google Scholar
  25. 24.
    Bauschlicher CW (1987) J Chem Phys 86:5591Google Scholar
  26. 25.
    Martin RL (1983) J Phys Chem 87:750; see also Cowan RD, Griffin DC (1976) J Opt Soc Am 66:1010Google Scholar
  27. 26.
    MOLECULE is a vectorized Gaussian integral program written by Almlöf JGoogle Scholar
  28. 27.
    SWEDEN is a vectorized SCF-MCSCF-direct CI-conventional CI-CPF-MCPF program, written by Siegbahn PEM, Bauschlicher Jr CW, Roos B, Taylor PR, Heiberg A, Almlöf J, Langhoff SR, Chong DPGoogle Scholar
  29. 28.
    Ahlrichs R, Scharf P, Jankowski K (1985) J Chem Phys 82:1413Google Scholar

Copyright information

© Springer-Verlag 1988

Authors and Affiliations

  • Charles W. BauschlicherJr
    • 1
  • Per Siegbahn
    • 2
  • Lars G. M. Pettersson
    • 2
  1. 1.NASA Ames Research CenterMoffett FieldUSA
  2. 2.Institute of Theoretical PhysicsUniversity of StockholmStockholmSweden

Personalised recommendations