红宝石中分子轨道效应和塞曼参数的确定

本文在配位场理论中利用普遍的静电相互作用参数,计算了红宝石吸收线的位置,结果比前人稍有改善。讨论了这些参数与分子轨道的关系,利用了二个共价键参数和自由离子参数,虽然引入的参数很少,但所得结果与上面的计算相近,并定出N_π≌0.92,N_σ≌0.89。计算了推广等效自旋哈密顿中的参数,发现修正项中的g因子是来自四级微扰的贡献,其数量级约为10^-5。得到了红宝石R线的等效哈密顿。

EFFECTS OF MOLECULAR ORBITALS AND CALCULATION OF THE ZEEMAN PARAMETERS IN RUBY

The positions of the absorption lines in ruby are calculated with the general electrostatic interaction parameters in the ligand-field theory. Consistence of the theory with experiment is slightly better than those obtained previously. The effects of molecular orbi-tals on these parameters are discussed. Similar results are obtained by a calculation using two covalence parameters and other known free-ion parameters. In this method, the calculated values of N_π≌0.92 and N_σ≌0.89 are obtained. The parameters in the generalized effective Spin-Hamiltonian are calculated. It is found that the g-factor in the modified term results from the contribution of the fourth order perturbation, and its order of magnitude is about 10^-5. The effective Hamiltonian which is used to describe the R line of ruby was obtained.