Optical Spectra of Divalent Manganese Salts. I. Energy Levels for Cubic and Lower‐Symmetry Complexes
Optical Spectra of Divalent Manganese Salts. I. Energy Levels for Cubic and Lower‐Symmetry Complexes
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DOI：
10.1063/1.1727379
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发表时间：
1966-11
影响因子：
4.4
通讯作者：
L. L. Lohr-L.
中科院分区：
文献类型：
--
作者：
L. L. Lohr-L.
介绍了Mn（II）盐的光学吸收光谱的广泛研究，重新审视了晶体场独立跃迁的性质及其对配体位置微小变化的依赖性。一个意想不到的，但显着减少金属配位体键长的4A2状态相对于那些6A1平衡基态的证据是从实验中得到的，在激发的全对称位移，并从近似计算。后者涉及的nephelauxetic效应和分子轨道（MO）参数的半经验LCAO MO计划获得的扩展配方。介绍了一种不一定在Mn（II）配合物中的与晶场无关的跃迁的分类方案，并且基于与跃迁能量相关的交换积分中出现的分子轨道类型，σ，π或两者。讨论了低对称性效应，特别是4E态。
An extensive study of the optical absorption spectra of Mn(II) salts is introduced with a re‐examination of the nature of crystal‐field independent transitions and their dependence upon slight changes in ligand positions. Evidence for an unexpected but significant decrease in metal—ligand bond lengths for the 4A2 state with respect to those for 6A1 equilibrium ground state is obtained both from experiment, in terms of the excitation of totally symmetric displacements, and from approximate calculations. The latter involve both an extended formulation of the nephelauxetic effect and molecular orbital (MO) parameters obtained by a semiempirical LCAO MO scheme. A classification scheme for crystal‐field independent transitions, not necessarily in Mn(II) complexes, is introduced, and is based on the type of molecular orbitals, σ, π, or both, appearing in the exchange integrals associated with the transition energies. Low‐symmetry effects, especially for the 4E states, are discussed.