Theoretica chimica acta

, Volume 74, Issue 6, pp 493–511 | Cite as

Vibrational partition functions for H2O derived from perturbation-theory energy levels

  • Alan D. Isaacson
  • Xing -Guo Zhang
Article

Abstract

Purely vibrational energy levels and partition functions are calculated using three different potential energy surfaces for the H2O molecule. Results obtained with perturbation-theory, independent-normal-mode (INM), and harmonic approximations are compared with accurate values. For the cases considered here, the expected improvement that perturbation theory provides over the corresponding harmonic treatment is found to be substantial, while the INM approximation leads to results which are worse than the corresponding harmonic ones. In fact, we show that reliable partition functions for these potential surfaces can be obtained when resonance contributions are removed from the perturbation-theory treatment, and we propose a theoretical criterion for deciding when a particular interaction should be treated as resonant.

Key words

Water Vibrational energy levels Partition functions Perturbation theory 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References and notes

  1. 1.
    Truhlar DG, Isaacson AD, Garrett BC (1985) Baer M (ed) The theory of chemical reaction dynamics, vol 4. CRC Press, Boca Raton p 1; this reference also contains a discussion of how normal-mode frequencies are obtained for a reacting complexGoogle Scholar
  2. 2.
    Garrett BC, Truhlar DG (1979) J Am Chem Soc 101:4534Google Scholar
  3. 3.
    Garrett BC, Truhlar DG (1979) J Phys Chem 83:1915Google Scholar
  4. 4.
    Isaacson AD, Truhlar DG, Scanlon K, Overend J (1981) J Chem Phys 75:3017Google Scholar
  5. 5.
    Isaacson AD, Truhlar DG (1981) J Chem Phys 75:4090Google Scholar
  6. 6.
    Isaacson AD, Truhlar DG (1982) J Chem Phys 76:1380Google Scholar
  7. 7.
    Isaacson AD, Truhlar DG (1984) J Chem Phys 80:2888Google Scholar
  8. 8.
    Nielsen HH (1959) Encycl Phys 37/1:173Google Scholar
  9. 9.
    Califano S (1976) Vibrational states. Wiley, LondonGoogle Scholar
  10. 10.
    Truhlar DG, Olsen RW, Jeannotte AC, Overend J (1976) J Am Chem Soc 98:2373Google Scholar
  11. 11.
    Carney GD, Sprandel LL, Kern CW (1978) Adv Chem Phys 37:305Google Scholar
  12. 12.
    Hoy AR, Mills IM, Strey G (1972) Mol Phys 24:1265Google Scholar
  13. 13.
    Romanowski H, Bowman JM (1985) “POLYMODE: program 496”, QCPE Bull 5(2):64Google Scholar
  14. 14.
    Harding LB, Ermler WC (1985) J Comput Chem 6:13Google Scholar
  15. 15.
    Bartlett RJ, Shavitt I, Purvis III GD (1979) J Chem Phys 71:281Google Scholar
  16. 16.
    Schatz GC, Elgersma H (1980) Chem Phys Lett 73:21Google Scholar
  17. 17.
    Pariseau MA, Suzuki I, Overend J (1965) J Chem Phys 42:2335Google Scholar
  18. 18.
    Carney GD, Kern CW (1975) Int J Quantum Chem Symp 9:317Google Scholar
  19. 19.
    Carney GD, Curtiss LA, Langhoff SR (1976) J Mol Spectrosc 61:371Google Scholar
  20. 20.
    Romanowski H, Bowman JM, Harding LB (1985) J Chem Phys 82:4155Google Scholar
  21. 21.
    Christoffel KM, Bowman JM (1982) Chem Phys Lett 85:220Google Scholar
  22. 22.
    Romanowski H, Bowman JM (1984) Chem Phys Lett 110:235Google Scholar
  23. 23.
    Romanowski H, private communicationGoogle Scholar
  24. 24.
    Papousek D, Aliev MR (1982) Molecular vibrational-rotational spectra. Elsevier, New York, pp 160–163Google Scholar
  25. 25.
    Schlegel HB, Wolfe S, Bernardi F (1977) J Chem Phys 67:4181Google Scholar
  26. 26.
    Nakagawa T, Morino Y (1968) J Mol Spectrosc 26:496; Nakagawa T, Morino Y (1969) Bull Chem Soc Jpn 42:2212Google Scholar
  27. 27.
    Isaacson AD, Truhlar DG, unpublished workGoogle Scholar
  28. 28.
    Kuchitsu K, Morino Y (1965) J Chem Soc Jpn 38:814Google Scholar

Copyright information

© Springer-Verlag 1988

Authors and Affiliations

  • Alan D. Isaacson
    • 1
  • Xing -Guo Zhang
    • 1
  1. 1.Department of ChemistryMiami UniversityOxfordUSA

Personalised recommendations