Rudowicz C
Biochim Biophys Acta. 1977 Feb 22;490(2):301-10. doi: 10.1016/0005-2795(77)90005-8.
The electronic structure of high-spin S = 2 ferrous ion in deoxy forms of hemoglobin and myoglobin is considered in terms of spin Hamiltonian formalism. Spin Hamiltonian parameters of the second order B0(2)(D), B2(2)(E) and, for the first time in the available literature, of fourth order B0(4), B2(4) and B4(4), are calculated for the rhombic symmetry case of Fe2+. The Hamiltonian matrix is diagonalized for several sets of Bq(k) parameters compatible with other experimental data. The low-lying Fe2+ levels exhibit crossings in a high magnetic field, applied along the z-axis perpendicular to the heme plane. The cross-over values of the magnetic field are determined to be Hc1 = 46 kOe and Hc2 = 168 kOe for D = 5.2, E = 0.6 cm-1 (close to the magnetic data of Nakano, N., Otsuka, J. and Tasaki, A. (1972) Biochim. Biophys. Acta 278, 355-371) and with B0(4) = 0.037, B2(4) = 0.005, B4(4) = 0.013 cm-1 and gz = 2.028. Experimental techniques for measurement of the crossing effects are discussed.
利用自旋哈密顿形式理论，研究了脱氧形式的血红蛋白和肌红蛋白中高自旋(S = 2)亚铁离子的电子结构。针对(Fe^{2 + })的菱形对称情况，计算了二阶自旋哈密顿参数(B_0^{(2)}(D))、(B_2^{(2)}(E))，以及在现有文献中首次出现的四阶参数(B_0^{(4)})、(B_2^{(4)})和(B_4^{(4)})。对与其他实验数据相符的几组(B_q^{(k)})参数，将哈密顿矩阵对角化。在垂直于血红素平面的(z)轴方向施加高磁场时，低能级的(Fe^{2 + })会出现能级交叉。对于(D = 5.2)、(E = 0.6 cm^{-1})（接近中野直、大冢纯和田崎昭（1972年）在《生物化学与生物物理学学报》278卷，355 - 371页中的磁性数据），且(B_0^{(4)} = 0.037)、(B_2^{(4)} = 0.005)、(B_4^{(4)} = 0.013 cm^{-1})以及(g_z = 2.028)的情况，确定交叉磁场值为(H_{c1} = 46 kOe)和(H_{c2} = 168 kOe)。讨论了测量交叉效应的实验技术。
