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Low spin ferric hemoglobin complexes

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Abstract

A caloulation has been made of the energy eigenfunotions and eigenvalues of low spin ferric ion in complexes with a strong cubic crystal field including the effects of tetragonal and rhombic distortions and of spin-orbit coupling among the ground state components and with excited states. Using the resultant, spin-orbit coupled eigenfunotions as a basis set, the magnetic susceptibility, the components of magnetic field energy, and the lattice and valence contributions to an electric field gradient at the iron nucleus were all calculated as a function of rhombic, tetragonal, and spin-orbit coupling strength used as parameters: R, u and δ. All of the calculated results agree reasonable well with experiment for the values of parameters R=1000 cm−1, u=2000 cm−1 and the free ion value (δ=420 cm−1. These values of parameters were selected for the excellent fit they gave of the calculated values of g x, gy and g z compared with the experimental ones obtained from single crystal electron spin resonance of ferrihemoglobin azide. With them, a value of 2.29 Bohr magnetons was calculated for the effective magnetic moment compared to the experimental value of 2.35. The total field gradient calculated under the same conditions, predicts a nuclear quadrupole moment Q in the range of. 107 –127. Barns, which is smaller than the range predicted from the high spin ferric ion results. Reasons for this discrepancy are discussed.

Zusammenfassung

Ausgehend von einem starken kubischen Ligandenfeld und unter Berücksichtigung tetragonaler (R) und rhombischer (u) Verzerrung sowie der Spin-Bahn-Kopplung (δ) werden Eigenfunktionen und Energien fur ‚Low-Spin‘-Ferrihämoglobinkomplexe berechnet. Mit den Parametern R=1000 cm−1, u=2000 cm−1, δ=420 cm−1 erhält man für Suszeptibilität, elektrischen Feldgradienten am Fe und g-Werte gute Übereinstimmung mit experimentellen Daten. Aus dem berechneten Feldgradienten folgt ein Quadrupolmoment des Fe57 von 0.107–0.127 Barn, im Gegensatz zu den viel höheren Resultaten bei ‚High-Spin‘-Fe(III)-Verbindungen; diese Diskrepanz wird diskutiert.

Résumé

Les fonctions propres et les énergies du complexe Ferrihémoglobine «low spin» sont calculées pour un fort champ de ligandes à symétrie cubique, en tenant compte des distortions tétragonale (R) et rhomboédrique (u), ainsi que du couplage spin-orbite (δ). Avec les parametres R=1000 cm−1, u=2000 cm−1, δ=420 cm−1, on trouve pour la susceptibilité, le gradient du champ électrique à l'emplacement de Fe et le facteur g des valeurs en bon accord avec les données expérimentales. On déduit du gradient de champ calculé un moment quadrupolaire de Fe57 de 0,107 à 0,127 Barn, en désaccord avec les résultats beaucoup plus élevés obtenus à partir des associations Fe (III) «high spin». Ce désaccord fait l'objet d'une discussion.

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Authors and Affiliations

  1. Hansen Laboratory of Biophysics, Stanford University, Stanford, California

    Gilda Harris

  2. Pomona CollegeDepartment of PhysicsClaremont, California, USA

    Gilda Harris

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  1. Gilda Harris
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Harris, G. Low spin ferric hemoglobin complexes. Theoret. Chim. Acta 5, 379–397 (1966). https://doi.org/10.1007/BF00527040

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