Advertisement

Theoretica chimica acta

, Volume 33, Issue 4, pp 285–297 | Cite as

Multi-configuration electron-hole potential method for excited states

  • Suehiro Iwata
  • Keiji Morokuma
Commentationes

Abstract

The recently proposed electron-hole potential (EHP) method for excited states is extended to the multi-configurational case. The variation equation is solved using the quadratic convergence method. The EHP methods are shown to be approximations to the complete singly excited configuration interaction (CSECI) in the variational sense. Extended Brillouin theorems are proved for the EHP methods. The excitation energies and wave functions obtained by one and two configurational EHP methods agree well with those of the CSECI method. The EHP methods have clear advantage in the computer time requirement over the CI method and are especially suited for a calculation of approximate excited states of large molecules. The EHP methods are applicable to excited states which belong to the same irreducible representation as the ground state.

Key words

Electron hole potential (EHP) method Complete singly excited configuration interaction Extended Brillouin theorems Excited states 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Roothaan,C.C.J.: Rev. Mod. Phys. 23, 69 (1951)Google Scholar
  2. 2.
    For example: Lathan, W.A., Curtiss, L.A., Hehre, W.J., Lisle, J.B., Pople, J.A.: Prog. Phys. Org. Chem., to be publishedGoogle Scholar
  3. 3.
    Roothaan,C.C.J.: Rev. Mod. Phys. 32, 179 (1960).Google Scholar
  4. 3a.
    Huzinaga,S.: Phys. Rev. 120, 866 (1960); 122, 131 (1961)Google Scholar
  5. 4. a)
    Iwata,S., Morokuma,K.: Unpublished;Google Scholar
  6. 4. b)
    Davidson,E.R.: Chem. Phys. Letters 21, 565 (1973)Google Scholar
  7. 5.
    Schaefer,H.F.III.: The electronic structure of atoms and molecules (Addison Wesley, 1972)Google Scholar
  8. 6.
    Shibuya,T., Rose,J., McKoy,V.: J. Chem. Phys. 58, 500 (1973)Google Scholar
  9. 7.
    Morokuma,K., Iwata,S.: Chem. Phys. Letters 16, 192 (1972)Google Scholar
  10. 8.
    Löwdin,P.O.: Phys. Rev. 97, 1490 (1955); Huzinaga,S., McWilliams,D., Contu,A.A.: Adv. Quant. Chem. 7, 187 (1973), and references thereinGoogle Scholar
  11. 9.
    Davidson,E.R.: J. Chem. Phys. 57, 1999 (1972)Google Scholar
  12. 10.
    Iwata,S., Morokuma,K.: Chem. Phys. Letters 19, 94 (1973)Google Scholar
  13. 11.
    Iwata,S., Morokuma,K.: J. Am. Chem. Soc. 95, 1563 (1973)Google Scholar
  14. 12.
    Iwata, S., Morokuma,K.: To be publishedGoogle Scholar
  15. 13.
    Lathan,W.A., Morokuma,K.: Presented at the Fifth Northeastern Regional Meeting, American Chemical Society at Rochester, N.Y., October 15–17, 1973Google Scholar
  16. 14.
    Bender,C.F., Dunning,T.H., Schaefer,H.F., Goddard,W.A., Hunt,W.J.: Chem. Phys. Letters 15, 171 (1972).Google Scholar
  17. 14a.
    Whitten,J.L.: J. Chem. Phys. 56, 5458 (1972).Google Scholar
  18. 14b.
    Morokuma,K, Konishi: J. Chem. Phys. 55, 402 (1971)Google Scholar
  19. 15. a)
    Roothaan,C.C.J., Bagus,P.S.: Methods in Comp. Phys. 2, 47 (1963).Google Scholar
  20. 15. b)
    Das,G., Wahl,A.C.: J. Chem. Phys. 56, 1769 (1972)Google Scholar
  21. 16.
    Hehre,W.J.,Lathan,W.A.,Ditchfield,R.,Newton,M.D., Pople,J.A.: Quantum chemistry program exchange, Indiana UniversityGoogle Scholar
  22. 17.
    Morokuma,K., Iwata,S., Lathan,W.A.: Presented by K.M. at the First International Congress of Quantum Chemistry, Menton, France, July 1973, and to be published in a book covering the Symposia of the CongressGoogle Scholar
  23. 18.
    Some of the linear equations proposed to solve the multi-configuration SCF do not satisfy the Hermiticity of Lagrange multipliers. For example: Ref. 15bGoogle Scholar
  24. 19.
    Dahl,J.P., Johansen,H., Truax,T.R., Ziegler,T.: Chem. Phys. Letters 6, 64 (1970)Google Scholar
  25. 20.
    Herzberg,G.: Electronic spectra, polyatomic molecules. Princeton: Van Nostrand 1966Google Scholar

Copyright information

© Springer-Verlag 1974

Authors and Affiliations

  • Suehiro Iwata
    • 1
  • Keiji Morokuma
    • 1
  1. 1.Department of ChemistryThe University of RochesterRochesterUSA

Personalised recommendations