Analysis of large-scale multi-configuration self-consistent field wave functions by expectation values of local operators
Analysis of large-scale multi-configuration self-consistent field wave functions by expectation values of local operators
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局部算子期望值分析大规模多构型自洽场波函数
DOI：
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发表时间：
1996
期刊：
影响因子：
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通讯作者：
H. Stoll
中科院分区：
文献类型：
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作者：
Martin Mödl;M. Dolg;P. Fulde;H. Stoll
我们发展了一种分析开壳系统多组态自洽场波函数的方法，它可能由非常多的Slate行列式组成，通过计算它们对(局部)单粒子和两粒子算符的期望值，以有效的数值方式。虽然所提出的形式是完全通用的，并且适用于任何涉及任意正交分子轨道子集的算符，但我们在这里使用的局域算符是根据定域分子轨道来定义的。这一选择允许对局部自旋、布居和电荷波动进行化学直观的分析，也允许研究化学键中的电子关联效应。我们介绍了一些离子和共价体系的应用，考虑了四个小分子，H2，N2，H2O和CH4，以及一个二元过渡金属络合物，[Fe2S6]6−。
We have developed a method to analyze multi‐configuration self‐consistent field wave functions for open‐shell systems, which may consist of a very large number of Slater determinants, by calculating their expectation values for (local) one‐ and two‐particle operators in a numerically efficient way. Although the proposed formalism is fully general and applies to any operators referring to a subset of arbitrary orthogonal molecular orbitals, the local operators we use here are defined in terms of localized molecular orbitals. This choice permits to perform a chemically intuitive analysis of the local spin, population and charge fluctuation, also allowing to study electron correlation effects in chemical bonding. We present some applications for ionic and covalent systems considering four small molecules, H2, N2, H2O and CH4, as well as a binary transition metal complex, [Fe2S6]6−.