Skip to main content
SpringerLink
Log in

Anomalous values of 〈Ŝ2〉 before and after annihilation of the first spin contaminant in UHF wave function

  • Published:
Journal of Structural Chemistry Aims and scope Submit manuscript

Abstract

We present a number of molecular systems for which the average values 〈Ŝ2〉 before and after annihilation of the first spin contaminant in the wave function of the unrestricted Hartree-Fock method are anomalously large (they substantially exceed the expected value S (S + 1)). An example of such systems is N@C20, for the doublet state of which the 〈Ŝ2〉 values are equal to 4.2595 before and 13.1390 after annihilation, respectively (calculated by UHF/6-31G* method). We show that four, at the least, spin multiplets (S′ = S, S + 1, S + 2, S + 3) contribute comparatively to the wave function of such systems. The relations are derived allowing one to estimate the contributions of the highest multiplets basing on the average values of 〈Ŝ2〉 before and after annihilation of the first spin contaminant.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. P. O. Löwdin, Advan. Chem. Phys., 2, 207 (1959).

    Google Scholar 

  2. J. E. Harriman, J. Chem. Phys., 40, 2827–2839 (1964).

    Article  CAS  Google Scholar 

  3. T. Amos and L. C. Snyder, ibid., 41, 1773–1783.

  4. A. V. Luzanov and N. S. Kulibaba, Teoret. Experim. Khim., J. Chem. Phys. 10, 147–154 (1974).

    Google Scholar 

  5. J. Tiňo and V. Klimo, Collection Czechoslov. Chem. Commun, 41, 3516–3520 (1976).

    Google Scholar 

  6. Y. G. Smeyers and A. M. Brucena, Int. J. Quantum Chem., 14, 641 (1978).

    Article  CAS  Google Scholar 

  7. A. D. Bacon and M. C. Zerner, Theoret. Chim. Acta., 53, 21–54 (1979).

    Article  CAS  Google Scholar 

  8. B. N. Plakhutin, Physical Mathematical Candidate’s Dissertation, Novosibirsk (1983).

  9. B. N. Plakhutin and G. M. Zhidomirov, in: Many-Electron Problem in Quantum Chemistry [in Russian], M. M. Mastechkin (ed.), Naukova Dumka, Kiev (1987).

    Google Scholar 

  10. J. S. Andrews, D. Jayatilaka, R. G. A. Bone, et al., Chem. Phys. Lett., 183, 423–431 (1991).

    Article  CAS  Google Scholar 

  11. D. Maurice and M. Head-Gordon, Int. J. Quantum. Chem., 29, 361–370 (1995).

    Article  CAS  Google Scholar 

  12. L. I. Trahtenberg, A. A. Fokeev, V. L. Klochikhin, et al., Khim. Fiz., 23, No. 6, 56–68 (2004).

    Google Scholar 

  13. M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al., Gaussian 98, Revision A.11, Pittsburgh PA (2001).

  14. B. N. Plakhutin, Information Materials of Specialized Foundation of Quantum Chemical Programs, Institute of Kinetics and Combustion, Sib. Otd. Akad. Nauk SSSR, 16/17 (1989).

  15. L. Noodleman, J. Chem. Phys., 74, 5737–5743 (1981).

    Article  CAS  Google Scholar 

  16. F. Sasaki and K. Ohno, J. Math. Phys., 4, 1140–1147 (1963).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Boreskov Institute of Catalysis, Siberian Division, Russian Academy of Sciences, Novosibirsk

    B. N. Plakhutin, M. A. Milov & T. E. Prokhorov

  2. International Tomography Center, Siberian Division, Russian Academy of Sciences, Novosibirsk

    E. V. Gorelik

  3. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow

    N. N. Breslavskaya & S. P. Dolin

  4. Karpov Research Physical-Chemical Institute, Moscow

    A.A. Fokeyev & L. I. Trakhtenberg

  5. Novosibirsk State University, Novosibirsk

    A. V. Novikov & N. E. Polygalova

Authors
  1. B. N. Plakhutin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. E. V. Gorelik
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. N. N. Breslavskaya
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. A. Milov
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. A.A. Fokeyev
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. A. V. Novikov
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. T. E. Prokhorov
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. N. E. Polygalova
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. S. P. Dolin
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. L. I. Trakhtenberg
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Original Russian Text Copyright © 2005 by B. N. Plakhutin, E. V. Gorelik, N. N. Breslavskaya, M. A. Milov, A. A. Fokeyev, A. V. Novikov, T. E. Prokhorov, N. E. Polygalova, S. P. Dolin, and L. I. Trakhtenberg

__________

Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 2, pp. 203–211, March–April, 2005.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Plakhutin, B.N., Gorelik, E.V., Breslavskaya, N.N. et al. Anomalous values of 〈Ŝ2〉 before and after annihilation of the first spin contaminant in UHF wave function. J Struct Chem 46, 195–203 (2005). https://doi.org/10.1007/s10947-006-0031-3

Download citation

  • Received:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10947-006-0031-3

Keywords

Search

Navigation