Russian Chemical Bulletin

, Volume 48, Issue 8, pp 1442–1449 | Cite as

Evaluation of a new procedure for quantum-chemical estimates of constants of isotropic hyperfine coupling with protons in free radicals

  • N. D. Chuvylkin
  • A. M. Tokmachev
Physical Chemistry
  • 18 Downloads

Abstract

A new procedure for quantum-chemical estimates of the constants of isotropic hyperfine coupling (IHFC) with protons using the orbital spin populations calculated in the basis set of symmetrically orthogonalized (according to Löwdin) atomic orbitals is tested taking 16 well-studied simplest π-electron and σ-electron radicals as examples. The most probable reasons for and possible ways of correcting large deviations of calculated IHFC constants from experimental values are considered. The efficiency of the semiempirical MNDORU scheme, which makes it possible to consistently estimate the delocalization and spin-polarization contributions to the constants of IHFC with protons in free radicals, is demonstrated.

Key words

ESR spectroscopy free radicals constants of isotropic hyperfine coupling with protons quantum-chemical estimates symmetrically orthogonalized basis set of atomic orbitals 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    H. Fisher, F. A. Neugebaer, and A. Berndt,Magnetic Properties of Free Radicals, in Landolt—Börnstein,Zahlenwerte und Funktionen aus Natrurwissenschaften und Technik, New Series II,17/b/c, Springer, Berlin, 1987.Google Scholar
  2. 2.
    C. Adamo, V. Barone, and A. Fortunelli,J. Chem. Phys., 1995,102, 384.CrossRefGoogle Scholar
  3. 3.
    G. M. Zhidomirov, P. V. Schastnev, and N. D. Chuvylkin,Kvantovo-khimicheskie raschety magnitno-rezonansnykh parametrov [Quantum-Chemical Calculations of Magnetic Resonance Parameters], Nauka, Novosibirsk, 1978, 368 pp. (in Russian).Google Scholar
  4. 4.
    P. Bischof and G. Friedrich,J. Comput. Chem., 1982,3, 486.CrossRefGoogle Scholar
  5. 5.
    C. Glidewell,J. Chem. Soc., Perkin Trans. 2, 1983,8, 1285.CrossRefGoogle Scholar
  6. 6.
    N. D. Chuvylkin, I. Yu. Shchapin, V. L. Klochikhin, V. A. Tikhomirov, and V. I. Fel'dman,Vestn. Mosk. Univ., Ser. 2, Khim., 1992,33, 307 [Moscow Univ. Bull., Ser. 2, Chem., 1992 (Engl. Transl.)].Google Scholar
  7. 7.
    N. D. Chuvylkin and A. M. Tokmachev,Izv. Akad. Nauk, Ser. Khim., 1999,48, 245 [Russ. Chem. Bull., 1999,48, 245 (Engl. Transl.)].Google Scholar
  8. 8.
    T. Clark,A Handbook of Computational Chemistry, J. Wiley and Sons, New York, 1985.Google Scholar
  9. 9.
    N. D. Chuvylkin, A. M. Tokmachev, A. V. Fionov, and E. V. Lunina,Izv. Akad. Nauk, Ser. Khim., 1997,46, 1743 [Russ. Chem. Bull., 1997,46, 1649 (Engl. Transl.)].Google Scholar
  10. 10.
    N. D. Chuvylkin, A. M. Tokmachev, A. V. Fionov, and E. V. Lunina,Mendeleev Commun., 1997,7, No. 5, 191.CrossRefGoogle Scholar
  11. 11.
    D. Feller and E. R. Davidson,J. Chem. Phys., 1984,80, 1006.CrossRefGoogle Scholar
  12. 12.
    J. S. Shirk and G. C. Pimentel,J. Am. Chem. Soc., 1968,90, 3349.CrossRefGoogle Scholar
  13. 13.
    J. F. Ogilvie,J. Mol. Struct., 1970,5, 157.CrossRefGoogle Scholar
  14. 14.
    I. Yu. Shchapin, V. I. Fel'dman, V. N. Belevskii, N. A. Donskaya, and N. D. Chuvylkin,Izv. Akad. Nauk, Ser. Khim., 1995,44, 212 [Russ. Chem. Bull., 1995,44, 203 (Engl. Transl.)].Google Scholar
  15. 15.
    I. Yu. Shchapin and N. D. Chuvylkin,Izv. Akad. Nauk, Ser. Khim., 1996,45, 321 [Russ. Chem. Bull., 1996,45, 306 (Engl. Transl.)].Google Scholar
  16. 16.
    R. W. Fessenden,J. Phys. Chem., 1967,71, 74.Google Scholar
  17. 17.
    W. J. Hehre, L. Radom, P. R. Schleyer, and J. A. Pople,Ab initio Molecular Orbital Theory, WIP, New York, 1986.Google Scholar
  18. 18.
    T. Yonezawa, H. Nakatsuji, T. Kawamura, and H. Kato,J. Chem. Phys., 1969,51, 669.CrossRefGoogle Scholar
  19. 19.
    J. A. Pople and M. Gordon,J. Am. Chem. Soc., 1967,89, 4253.CrossRefGoogle Scholar
  20. 20.
    H. S. Judeikis and S. Siegel,J. Chem. Phys., 1965,43, 3625.CrossRefGoogle Scholar

Copyright information

© Kluwer Academic/Plenum Publishers 1999

Authors and Affiliations

  • N. D. Chuvylkin
    • 1
  • A. M. Tokmachev
    • 2
  1. 1.N. D. Zelinsky Institute of Organic ChemistryRussian Academy of SciencesMoscowRussian Federation
  2. 2.Department of ChemistryM. V. Lomonosov Moscow State UniversityMoscowRussian Federation

Personalised recommendations