ACCURATE EMPIRICAL SPIN-ORBIT-COUPLING PARAMETERS ZETA(ND) FOR GASEOUS ND(Q) TRANSITION-METAL IONS - THE PARAMETRICAL MULTIPLET TERM MODEL
ACCURATE EMPIRICAL SPIN-ORBIT-COUPLING PARAMETERS ZETA(ND) FOR GASEOUS ND(Q) TRANSITION-METAL IONS - THE PARAMETRICAL MULTIPLET TERM MODEL
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DOI：
10.1021/ic00065a010
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发表时间：
1993-06-23
影响因子：
4.6
通讯作者：
SCHAFFER, CE
中科院分区：
文献类型：
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作者：
BENDIX, J;BRORSON, M;SCHAFFER, CE
提供了一个全面和最新的化学相关的原子nd（q）系统的单电子自旋轨道耦合参数zeta（nd）的列表。结果是从有效算子分析，项目的经验nd（q）数据的一个完整的参数化至于本征值和本征态的配置的多重态项有关。唯一的附加参数是zeta（nd）。在文献的语言中，我们已经对实验上充分已知的d3、d4、d5、d 6和d 7系统进行了数学上完全的库仑分析。这是40年前对d2和dg所做的，而从那时起，对其他dq系统的扩展已经被多次尝试过。虽然该方法不是以简单的方式与第一原理相关，但它不仅仅是一种使用明确定义的程序的数据简化机器。因此，给定ndq系统的模型参数可解释为多项能量和zeta（nd）。因此，不仅该过程的参数结果作为指导，以学术综述周期表，但其参数值也可以作为参考值在配位场和磁性的背景下。本方法的优点在于其与用于获得zeta（nd）值的当前方法的直接关系，即，使用Lande间隔规则或Slater-Condon-Shortley模型。本文包括本模型的Slater-Condon-Shortley框架，它不再可以被认为是一个传统的物理模型，但仍然可以务实地使用相当大的成功的讨论。相互正交的运营商集服务于我们的分析作为一个概念和实用的工具。然而，它表明，使用正交集的运营商并不意味着他们的相关参数将是不相关的，但它使相关性分析更加透明。一般的结论是，所有的化学相关的nd（q）系统是参数化的，相当准确，并在化学上有用的方式。
A comprehensive and up-to-date tabulation of one-electron spin-orbit coupling parameters zeta(nd) for atomic nd(q) systems of chemical relevance is provided. The results are obtained from an effective-operator analysis that projects out of the empirical nd(q) data a complete parametrization as far as eigenvalues and eigenstates of the configuration's multiplet terms are concerned. The only additional parameter is zeta(nd). In the language of the literature we have made the Coulomb analysis mathematically complete for the experimentally sufficiently known d3, d4, d5, d6, and d7 systems. This was done 40 years ago for d2 and dg, while an extension to other dq systems has been approached many times ever since. Although the method is not in a simple way related to first principles, it is not merely a data-reduction machinery using a well-defined procedure. Thus, the model parameters for a given ndq System are interpretable as the multiplet-term energies and zeta(nd). Therefore, not only do the procedure's parametric results serve as a guide to academic overviews over the periodic table but its parameter values may also serve as reference values in ligand-field and magnetism contexts. The present method has an advantage in its straightforward relationship with current methods for obtaining zeta(nd) values, viz. the use of the Lande interval rule or of the Slater-Condon-Shortley model. The paper includes a discussion of the present model in relation to the Slater-Condon-Shortley framework, which no longer can be considered a conventional physical model but still can be used pragmatically with considerable success. Sets of mutually orthogonal operators have served our analyses both as a conceptual and a practical tool. It is, however, demonstrated that the use of orthogonal sets of operators does not imply that their associated parameters will be uncorrelated, but it makes the correlation analysis more transparent. The general conclusion is that all nd(q) systems of chemical relevance are parametrizable, quite accurately and in a chemically useful way.