Seth Michael, Krykunov Mykhaylo, Ziegler Tom, Autschbach Jochen
Department of Chemistry, University of Calgary, University Drive 2500, Calgary AB T2N-1N4, Canada.
J Chem Phys. 2008 Jun 21;128(23):234102. doi: 10.1063/1.2933550.
The magnetically perturbed time-dependent density functional theory is used to derive equations for the magnetic circular dichroism (MCD) of degenerate transitions of closed shell molecules. The MCD of this type of transition can be divided into two contributions. The dominant contribution is usually that from A terms that arise because of the breaking of the degeneracy of the excited state in the presence of the magnetic field. The second contribution comes from B terms that arise because of the perturbation of the transition dipole by the magnetic field. The formalism is applied to ten tetrahedral d(0) transition metal oxy- and thioanions. The MCD parameters of these systems are reproduced quite well by the calculations. Simulated spectra derived from the calculated parameters are in good agreement with the observed spectra.
利用磁微扰含时密度泛函理论推导闭壳层分子简并跃迁的磁圆二色性（MCD）方程。这类跃迁的MCD可分为两种贡献。主要贡献通常来自A项，它是由于在磁场存在下激发态简并性的破坏而产生的。第二种贡献来自B项，它是由于磁场对跃迁偶极矩的微扰而产生的。该形式体系应用于十个四面体d(0)过渡金属氧阴离子和硫阴离子。计算结果很好地再现了这些体系的MCD参数。由计算参数得到的模拟光谱与观测光谱吻合良好。
