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Non-orthogonal internally contracted multi-configurational perturbation theory (NICPT): Dynamic electron correlation for large, compact active spaces
The Journal of Chemical Physics ( IF 4.4 ) Pub Date : 2017-11-06 , DOI: 10.1063/1.4999218
Sven Kähler 1 , Jeppe Olsen 1
Affiliation  

A computational method is presented for systems that require high-level treatments of static and dynamic electron correlation but cannot be treated using conventional complete active space self-consistent field-based methods due to the required size of the active space. Our method introduces an efficient algorithm for perturbative dynamic correlation corrections for compact non-orthogonal MCSCF calculations. In the algorithm, biorthonormal expansions of orbitals and CI-wave functions are used to reduce the scaling of the performance determining step from quadratic to linear in the number of configurations. We describe a hierarchy of configuration spaces that can be chosen for the active space. Potential curves for the nitrogen molecule and the chromium dimer are compared for different configuration spaces. Already the most compact spaces yield qualitatively correct potentials that with increasing size of configuration spaces systematically approach complete active space results.

中文翻译:

非正交内部收缩的多构型扰动理论(NICPT):大型紧凑活动空间的动态电子相关性

针对需要对静态和动态电子相关性进行高级处理,但由于所需的有源空间大小而无法使用常规的完整有源空间自洽场方法进行处理的系统,提出了一种计算方法。我们的方法引入了一种有效的算法,用于紧凑型非正交MCSCF计算的微扰动态相关校正。在该算法中,使用轨道的正交正交扩展和CI波函数来减少性能确定步骤的配置数量从二次到线性的缩放。我们描述了可以为活动空间选择的配置空间的层次结构。比较了不同构型空间下氮分子和铬二聚体的电势曲线。
更新日期:2017-11-07
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