Multiconfiguration optimized effective potential method for a density-functional treatment of static correlation.
Multiconfiguration optimized effective potential method for a density-functional treatment of static correlation.
复制标题
用于静态相关性密度泛函处理的多配置优化有效势方法。
DOI：
10.1063/1.2868755
复制
发表时间：
2008
期刊：
影响因子：
--
通讯作者：
A. Görling
中科院分区：
文献类型：
--
作者：
M. Weimer;F. Della Sala;A. Görling
提出了一种在密度泛函框架内处理静态相关性的方法。为此，导出了多配置优化有效电位（MCOEP）方法。与标准多配置自洽场 (MCSCF) 方法以及以前的 MCSCF 程序与密度泛函理论的组合相比，MCOEP 方法产生明确定义的物理有意义的轨道和特征值谱。除了电子基态之外，还可以描述激发电子态。 MCOEP 方法是通过调用局部 Hartree-Fock 近似来实现的，从而产生多配置局部 Hartree-Fock 方法。新方法在氢分子解离以及乙烯和环丁二烯异构化中的应用表明，它能够描述具有强静态相关性的情况。
An approach to treat static correlation within a density-functional framework is presented. To that end, a multiconfiguration optimized effective potential (MCOEP) method is derived. In contrast to standard multiconfiguration self-consistent field (MCSCF) methods and previous combinations of MCSCF procedures with density-functional theory, the MCOEP method yields well-defined physically meaningful orbital and eigenvalue spectra. In addition to the electronic ground state also excited electronic states can be described. The MCOEP method is implemented invoking the localized Hartree-Fock approximation, leading to a multiconfiguration localized Hartree-Fock approach. Applications of the new method to the dissociation of the hydrogen molecule and the isomerization of ethene and cyclobutadiene show that it is capable of describing situations that are characterized by strong static correlation.