Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Theory of isomer shift in hemin

  • 28 Accesses

  • 6 Citations

Abstract

Using the self-consistent charge extended Hückel procedure, the charge density difference Δϱ at Fe57 nucleus, between hemin and Fe+3 ion is calculated. This is combined with the recent value of the calibration constant, −0.23±0.02a 0 3 mm/sec to obtain an isomer shift of −0.374 mm/sec between hemin and Fe+3 in good agreement with the value −0.392 mm/sec derived from experimental data and the calculated value of the isomer shift of Fe+3 with respect to K3FeF6 from first principle covalency investigations in the latter compound. Δϱ is composed of contributions from core and valence electrons of the same order of magnitude, with the latter being more than one-half of the former. The core contribution is composed of a number of terms of comparable magnitude and differing signs, whose significance is discussed.

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

References

  1. 1.

    Han,P.S., Das,T.P., Rettig,M.F.: J. Chem. Phys.56, 3861 (1972)

  2. 2.

    Han,P.S., Rettig,M.F., Ikenberry,D., Das,T.P.: Theoret. Chim. Acta (Berl.)22, 261 (1971)

  3. 3.

    Han,P.S., Das,T.P., Rettig,M.F.: Theoret. Chim. Acta (Berl.)16, 1 (1970)

  4. 4.

    Rettig,M.F., Han,P.S., Das,T.P.: Theoret. Chim. Acta (Berl.)12, 178 (1968); Erratum. Theoret. Chim. Acta (Berl.)13, 432 (1969)

  5. 5.

    Zerner,M., Gouterman,M., Kobayashi,H.: Theoret. Chim. Acta (Berl.)6, 363 (1966); Zerner,M., Gouterman,M.: Theoret. Chim. Acta (Berl.)4, 44 (1966)

  6. 6.

    Chang,J.C., Das,T.P., Ikenberry,D.: Theoret. Chim. Acta (Berl.)35, 361 (1974)

  7. 7.

    Hoffman,R.: J. Chem. Phys.39, 1397 (1963)

  8. 8.

    Koenig,D.F.: Acta Cryst.18, 663 (1965)

  9. 9.

    Mulliken,R.S.: J. Chem. Phys.23, 1833 (1955)

  10. 10.

    Duff,K.J., Das,T.P.: Phys. Rev.B3, 192; 2294 (1971)

  11. 11.

    Shirley,D.A.: Rev. Mod. Phys.36, 339 (1964)

  12. 12.

    Duff,K.J.: Phys. Rev.B9, 66 (1974)

  13. 13.

    Micklitz,H., Litterst,F.L.: Phys. Rev. Letters33, 480 (1974); Trautwein,A., Harris,F.E., Freeman, A.J., Desclaux,J.P.: Phys. Rev. (in press)

  14. 14.

    Ray,S.N., Lee,T., Das,T.P.: Phys. Rev.B12, 58 (1975)

  15. 15.

    Gonser,U., Grant,R.W.: Biophys. J.5, 823 (1965)

  16. 16.

    Champion,V.I., Vaughan,R.W., Drickamer,H.G.: J. Chem. Phys.47, 2583 (1967)

  17. 17.

    Danon,J., in: Chemical applications of Mössbauer spectroscopy, Chapt. 3, Tables 3.28 and 3.34. Goldanski, V.I. and Herber,R.H., Eds. New York: Academic Press,

  18. 18.

    Gourary,B.S., Adrian,F.J.: Phys. Rev.105, 1180 (1957). See also Ikenberry,D., Das,T.P.: Phys. Rev.B1, 1219 (1970) and Refs. therein

  19. 19.

    The Hartree-Fock functions used for ferric ion were kindly supplied by Dr. J. B. Mann, Radiation Laboratory of University of California, Los Alamos, New Mexico (1968)

  20. 20.

    Such a model has been used in recent calculations by Sharma,R.R. and Moutsos,P. as reported in Bull. Amer. Phys. Soc.19, 1101 (1974). See also Moutsos,P., Adams III,J.G. and Sharma,R.R.: J. Chem. Phys.60, 1447 (1974). They consider only the Pauli effect arising from overlap of the Fe+3 ions with the atomic orbitals of the nitrogen, chlorine and carbon atoms. K. J. Duff (J. Chem. Phys.63, 2259 (1975)) has recently commented on the difficulties in the approach used by the authors.

  21. 21.

    Ikenberry,D., Das,T.P.: Phys. Rev.184, 989 (1969)

  22. 22.

    Bearden,A.J., Moss,T.H., Caughey,W.S., Beaudreau,C.A.: Proc. Natl. Acad. Sci. U.S.53, 1246 (1965)

  23. 23.

    Lang,G., Marshall,W.: Proc. Phys. Soc.87, 3 (1966)

Download references

Author information

Additional information

Supported by grant HL 15196-02 from the Heart and Lung Institute of National Institute of Health.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Chang, J.C., Kim, Y.M., Das, T.P. et al. Theory of isomer shift in hemin. Theoret. Chim. Acta 41, 37–49 (1976). https://doi.org/10.1007/BF00558022

Download citation

Key word

  • Hemin, isomer shift in ∼