Advertisement

Theoretica chimica acta

, Volume 35, Issue 4, pp 277–292 | Cite as

PNO-CI and CEPA studies of electron correlation effects

II. Potential curves and dipole moment functions of the OH radical
  • Wilfried Meyer
Commentationes

Abstract

Ab initio calculations of the potential curves of low laying electronic states of OH are performed on the basis of a variational configuration interaction wavefunction (PNO-CI) and the coupled electron pair approximation (CEPA).

The latter approach yields a ground state potential curve which deviates from the RKR curve by less than 200 cm−1 in the region from 0.7 to 1.6 Å. Calculated ground state constants are as follows (experimental values in parentheses): re = 0.972 (0.971) Å, Be = 18.85 (18.87) cm−1, α e = 0.727 (0.714) cm−1, ω e = 3742 (3739) cm−1, ω e χ e = 85.3 (86.4) cm−1, μ0 = 1.686 (1.66) D, D e = 4.35 (4.63) eV,IP = 12.78 (13.36?) eV, El.Aff. = 1.51 (1.83) eV, v00(2Π↔2Σ+) = 32690(32440) cm−1.

The correlation contributions to ionization, excitation and electron attachment are analyzed. On the basis of estimated CEPA-limits, which are in very good agreement with experiment for D e and electron affinity, an IP of 13.0eV is recommended. Dipole moment expectation values and some IR transition probabilities are calculated from the ground state dipole moment curves. The calculated crossing point of the 2Σ curve with the repulsive 4Σ state is not in agreement with the position deduced from intensity data.

Key words

OH-radial, potential curves of ∼, dipole moments of ∼ 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Meyer,W.: Intern. J. Quantum Chem. S 5, 341 (1971)CrossRefGoogle Scholar
  2. 2.
    Meyer,W.: J. Chem. Phys. 58, 1017 (1973)CrossRefGoogle Scholar
  3. 3.
    Das,G., Wahl, A.C.: J. Chem. Phys. 44, 87 (1966)CrossRefGoogle Scholar
  4. 3.a
    Wahl,A.C., Das,G.: Advan. Quantum Chem. 5, 261 (1970)CrossRefGoogle Scholar
  5. 3.b
    Das,G., Wahl,A.C.: J. Chem. Phys. 56, 1769 (1971)CrossRefGoogle Scholar
  6. 4.
    Hinze,J.A., Roothaan,C.C.: Progr. Theoret. Phys. 40, 37 (1967)CrossRefGoogle Scholar
  7. 4.a
    Levy,B.: Intern. J. Quantum Chem. 4, 297 (1970)CrossRefGoogle Scholar
  8. 5.
    Harris,F.E., Michels,H.H.: Intern. J. Quantum Chem. S1, 329 (1967)Google Scholar
  9. 6.
    Michels,H.H., Harris,F.E.: Chem. Phys. Letters 3, 441 (1969)CrossRefGoogle Scholar
  10. 7.
    Schaefer,H.F.: J. Chem. Phys. 54, 2207 (1971)CrossRefGoogle Scholar
  11. 7.a.
    Pearson,P.K., Bender,C.F., Schaefer,H.F.,III: J. Chem. Phys. 55, 5235 (1971)CrossRefGoogle Scholar
  12. 7.b
    O'Neil,S.V., Schaefer,H.F.: J. Chem. Phys. 55, 394 (1971)CrossRefGoogle Scholar
  13. 8.
    Bondybey,V., Pearson,P.K., Schaefer,H.F.: J. Chem. Phys. 57, 1123 (1972)CrossRefGoogle Scholar
  14. 9.
    Kelly,H.P.: Phys. Rev. 134A, 1450 (1964); 136B, 896 (1964)CrossRefGoogle Scholar
  15. 10.
    Goldstone,J.: Proc. Roy. Soc. (London) A239, 267 (1957)CrossRefGoogle Scholar
  16. 11.
    Cade,P.E., Huo,W.M.: J. Chem. Phys. 47, 614 (1967)CrossRefGoogle Scholar
  17. 12.
    Huzinaga,S.: J. Chem. Phys. 42, 1293 (1965)CrossRefGoogle Scholar
  18. 13.
    Fallon,R.J., Tobias,I., Vanderslice,J.T.: J. Chem. Phys. 34, 167 (1961) Schäfer,J.: Private communicationCrossRefGoogle Scholar
  19. 14.
    Bender,C.F., Davidson,E.R.: Phys. Rev. 138, 23 (1969)CrossRefGoogle Scholar
  20. 15.
    Mehler,E.: Theoret. chim. Acta (Berl.) 35, 17 (1974)CrossRefGoogle Scholar
  21. 16.
    Chamberlain,J.W., Roessler,F.L.: Phys. Rev. 58, 541 (1954)Google Scholar
  22. 17.
    Meyer,W., Rosmus,P.: To be publishedGoogle Scholar
  23. 18.
    Cade,P.E.: J. Chem. Phys. 47, 2390 (1967)CrossRefGoogle Scholar
  24. 19.
    Siebert,H.: Anwendungen der Schwingungsspektroskopie. Wien: Springer 1966CrossRefGoogle Scholar
  25. 20.
    Silverstone,H.J., Sinanoğlu.,O.: J. Chem. Phys. 44, 1898, 3608 (1966)Google Scholar
  26. 21.
    Brandscomb,L.M.: Phys. Rev. 148 (1966)Google Scholar
  27. 22.
    Gaydon, A.G., Wolfhard,H.G.: Proc. Roy. Soc. A 208, 63 (1951)CrossRefGoogle Scholar
  28. 23.
    Naegeli,D.W., Palmer,H.B.: J. Mol. Spectr 23, 44 (1967)CrossRefGoogle Scholar
  29. 24.
    Mulder,J.: Unpublished resultsGoogle Scholar
  30. 25.
    Ferguson,F., Parkinson,D.: Planet. Space Sci. 11, 149 (1963)CrossRefGoogle Scholar
  31. 26.
    Murphy,R.E.: J. Chem. Phys. 54, 4852 (1971)CrossRefGoogle Scholar
  32. 27.
    Green,S.: J. Chem. Phys. 58, 4327 (1972)CrossRefGoogle Scholar
  33. 28.
    Scarl,E.A., Dalby,F.W.: Can. Phys. Soc. 49, 2825 (1971)CrossRefGoogle Scholar
  34. 29.
    Weinstock,E.M., Zare,R.N.: J. Chem. Phys. 58, 4319 (1972)CrossRefGoogle Scholar
  35. 30.
    Herzberg, G.: Spectra of diatomic molecules. Princeton: Van Nostrand 1950Google Scholar
  36. 31.
    Karo,A., Krauss,M., Wahl,A.C.: Intern. J. Quantum Chem. S 7, 143 (1973)CrossRefGoogle Scholar
  37. 32.
    Powell,F.X., Lide,D.R.: J. Chem. Phys. 42, 4201 (1965)CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 1974

Authors and Affiliations

  • Wilfried Meyer
    • 1
  1. 1.Institut für Physikalische Chemie der Universität MainzGermany

Personalised recommendations