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Orbital correlation effects: The independent pair-potential approximation with application to the ground state and first ionized state of boron hydride

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Abstract

A new method is proposed for calculating correlation effects in atomic and molecular systems. The basis of the method is the formulation of a set of partial configuration expansions which yield directly variational orbital correlation corrections which are appropriately summed in order to obtain an estimate of the total correlation energy. This method is applied to the ground state of boron hydride and its cation at the equilibrium distance of BH. The results of the method are compared in detail with independent electron pair results and second order CI results. It is further shown that multiple substitutions are approximately accounted for in this method and the extent to which they are included is compared with other approximations. Finally, three methods of increasing accuracy, aimed at reducing the necessary computational effort, are given for determining the vertical ionization potential. The most economical method yields an IP of 9.70 eV or 0.03 eV less than the experimental IP. Completion of the basis is estimated to improve this value to 9.77 eV.

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References

  1. Rodberg,L.S.: Ann. of Phys.2, 199 (1957)

    Article  Google Scholar 

  2. Brueckner, K.A., Levinson,C.A., Mahmoud,H.: Phys. Rev.95, 217 (1954); Brueckner,K.A.: Phys. Rev.96, 508 (1954);97, 1353 (1955); Brueckner,K.A, Levinson,C.A.: Phys. Rev.97, 1344 (1955)

    Article  CAS  Google Scholar 

  3. Sinanoglu,O.: J. Chem. Phys.36, 706 (1962); 3198 (1962); Advan. Chem. Phys.14, 237 (1969)

    CAS  Google Scholar 

  4. Nesbet,R.K.: Advan. Chem. Phys.9, 321 (1965);14, 1 (1969)

    CAS  Google Scholar 

  5. Nesbet,R.K.: Phys. Rev.109, 1632 (1958); Int. J. Quantum Chem.4, 117 (1971)

    CAS  Google Scholar 

  6. Kutzelnigg, W. in: Selected topics in molecular physics (E. Clementi, Ed.) pp. 91–102. Weinheim: Verlag Chemie 1972

    Google Scholar 

  7. Nesbet,R.K.: Phys. Rev.155, 51, 56 (1967);175, 2 (1968);3A, 87 (1971)

    CAS  Google Scholar 

  8. Tuan,D.F., Sinanoglu,O.: J. Chem. Phys.41, 2672 (1964); McKoy,V., Sinanoglu,O.: J. Chem. Phys.41, 2689(1964)

    Article  Google Scholar 

  9. Öksuz,I., Sinanoglu,O.: Phys. Rev.181, 42, 54 (1969)

    Google Scholar 

  10. Viers,A.W., Harris,F.E., Schaefer,H.F. III: Phys. Rev.1A, 24 (1970)

    Google Scholar 

  11. Weiss, A.W.: Phys. Rev.3A, 126 (1971)

    Google Scholar 

  12. Ahlrichs,R., Kutzelnigg,W.: Theoret. Chim. Acta (Berl.)10, 377 (1968)

    Article  CAS  Google Scholar 

  13. Gélus,M.,Ahlrichs,R.,Staemmler,V., Kutzelnigg,W.: Theoret. Chim. Acta (Berl.)21, 63 (1971)

    Article  Google Scholar 

  14. Van Der Velde,G. A., Nieuwpoort,W.C.: Chem. Phys. Letters13, 409 (1972)

    Google Scholar 

  15. Lischka,H.: Theoret. Chim. Acta (Berl.)31, 39 (1973); Staemmler,V.: Theoret. Chim. Acta (Berl.)31, 49 (1973)

    Article  CAS  Google Scholar 

  16. Barr,T.L., Davidson,E.R.: Phys. Rev. A1, 644 (1970)

    Article  CAS  Google Scholar 

  17. Nesbet,R.K., Barr,T.L., Davidson,E.R.: Chem. Phys. Letters4, 203 (1969)

    CAS  Google Scholar 

  18. Meyer,W.: J. Chem. Phys.58, 1017 (1973); Int. J. Quantum Chem. S5, 341 (1971)

    Article  CAS  Google Scholar 

  19. Mehler,E.L. in: Papers, International Conference on Computers in Chemical Research and Education, Ljubljana, Yugoslavia 1973

  20. Nesbet,R.K.: Phys. Rev.109, 1632 (1958)

    CAS  Google Scholar 

  21. Szasz,L.: Z. Naturforschung14a, 1014 (1959)

    CAS  Google Scholar 

  22. Bender,C.F., Davidson,E.R.: Phys. Rev.183, 23 (1969)

    Article  CAS  Google Scholar 

  23. Cade,P.E., Huo,W.M.: J. Chem. Phys.45, 1063 (1966)

    Article  CAS  Google Scholar 

  24. Mehler,E.L.: Int. J. Quantum Chem.7S, 437 (1973)

    Google Scholar 

  25. Bender,C.F., Davidson,E.R.: J. Phys. Chem.70, 2675 (1966)

    CAS  Google Scholar 

  26. Musher,J.I.: Theoretical chemistry Series One,1, W.B. Brown Ed.) p. 1–40. Baltimore: University Park Press. Wahl,A.C: ibid. pp. 41–70

  27. Mehler,E. L., v. d. Velde,G., Nieuwpoort, W. C.: To be published

  28. Mehler,E.L., Ruedenberg,K.R., Silver,D.M.: J. Chem. Phys.52, 1181 (1970)

    Article  CAS  Google Scholar 

  29. Davidson,E.R., Bender,CF.: J. Phys. Chem.49, 465 (1968)

    CAS  Google Scholar 

  30. Bender,C.F.,Davidson,E.R.: Chem. Phys. Letters3, 33 (1969)

    CAS  Google Scholar 

  31. Davidson,E.R., Bender,C.F.: J. Chem. Phys.56, 4334 (1972)

    Article  CAS  Google Scholar 

  32. Boys,S.F. in: Quantum theory of atoms, molecules, and the solid state, P.O.Löwdin Ed., p.253. New York: Interscience 1967

    Google Scholar 

  33. Brenig,W.: Nucl. Phys.4, 363 (1957)

    Google Scholar 

  34. Kelly,H.P.: Advan. Chem. Phys.14, 129 (1969)

    CAS  Google Scholar 

  35. Verhaegen,G., Bergen,J.J., Deslaux,J.P., Moser,C.M.: Chem. Phys. Letters9, 479 (1971)

    CAS  Google Scholar 

  36. Moser,C. M., Nesbet,R.K., Verhaegen,G.: Chem. Phys. Letters12, 230 (1971)

    CAS  Google Scholar 

  37. Sinanoglu,O., Tuan,D.F.: J. Chem. Phys.38, 1740 (1963)

    CAS  Google Scholar 

  38. Paldus,J., Cizek,J., Shavitt,I.: Phys. Rev.5A, 50 (1972)

    Google Scholar 

  39. Wilkinson,P.G.: Astrophys. J.138, 778 (1963)

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Laboratory of Structural Chemistry, University of Groningen, Groningen, The Netherlands

    E. L. Mehler

  2. Biozentrum, Universität Basel, Klingelbergstraße 70, CH-4056, Basel, Switzerland

    E. L. Mehler

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  1. E. L. Mehler
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Mehler, E.L. Orbital correlation effects: The independent pair-potential approximation with application to the ground state and first ionized state of boron hydride. Theoret. Chim. Acta 35, 17–32 (1974). https://doi.org/10.1007/BF02394556

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  • DOI: https://doi.org/10.1007/BF02394556

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