First principles electronic structure investigation of order of singlet and triplet states of oxyhemoglobin and analysis of possible influence of muon trapping

Interest in the possibility of magnetic character for oxyhemoglobin (OxyHb) has been recently stimulated by the observations of muon spin-lattice relaxation effects studied (Nagamine et al., Proc Jpn Acad Ser B Phys Biol Sci 83:120-126, 2007) with the muon-spin rotation (μSR) technique. In view of this, we have carried out first-principles electronic structure investigations involving Hartree-Fock theory combined with many body perturbation effects for the singlet and triplet states of OxyHb. Our results indicate that using two recent x-ray structural data (Paoli et al., J Mol Biol 256:775, 1996; Park et al., J Mol Biol 360:690, 2006) for OxyHb, for only Hartree-Fock theory without many-body effects included, the singlet state lies above the triplet state by energies of about 0.08 and 0.13 a. u. for the two structures in Paoli et al. (J Mol Biol 256:775, 1996) and Park et al. (J Mol Biol 360:690, 2006). Incorporation of many-body effects by the perturbation method reverses the order, with the triplet state located 0.18 and 0.14 a. u. above the singlet state for the structures in Paoli et al. (J Mol Biol 256:775, 1996) and Park et al. (J Mol Biol 360:690, 2006). Physical reasons for these relative orderings of the singlet and triplet states will be discussed. It is clear that OxyHb by itself would be in a singlet state at room temperature or below, since from our calculation, the triplet state lies about KT above the singlet state with T having the value of 44,098 K and 56,449 K for the two structural data in Paoli et al. (J Mol Biol 256:775, 1996) and Park et al. (J Mol Biol 360:690, 2006). As regards the muon spin-lattice relaxation effects obtained by recent μSR measurements (by Nagamine et al., Proc Jpn Acad Ser B Phys Biol Sci 83:120-126, 2007) at room temperature, the sensitive dependence of the singlet-triplet separation on many-body effects in our investigation suggests that it is possible that the singlet-triplet separation could be reversed or reduced significantly when a muon is trapped near an oxygen atom of the oxygen molecule, allowing the triplet to be occupied at room temperature and lead to significant muon spin-lattice relaxation.