论文标题

通过NOF近似值,铁(II)卟啉中的电子相关性

Electron correlation in the Iron(II) Porphyrin by NOF approximations

论文作者

Lew-Yee, Juan Felipe Huan, del Campo, Jorge M., Piris, Mario

论文摘要

铁(II)卟啉(FEP)的单线,三重态和五重奏自旋状态的相对稳定性代表了电子结构方法的挑战性问题。虽然目前可以接受基态是三重态,但基于多配制波函数的方法可以预测五重奏,而密度函数近似在三重态和五重状态之间有所不同,导致预测高度取决于所采用方法的特征。最近提出的全球天然轨道功能(GNOF)旨在在静态和动态相关性之间提供平衡的处理,以及先前的Piris天然轨道功能(PNOFS),使我们能够探索每种类型的相关性在FEP的稳定性顺序中的重要性,并保存FEP的稳定性顺序。值得注意的是,GNOF将所有可用轨道中的所有电子在给定的基础集中相关联;对于本工作中使用的双重zeta基序的FEP;这意味着GNOF可以在465个轨道中正确地关联186个电子,从而显着增加了适合多种配置处理的系统的尺寸。结果表明,PNOF5,PNOF7S和PNOF7预测五重奏的能量低于三重态。但是,通过二阶moller-plesset校正(NOF-MP2)增加动态相关性的使三重态更低,而GNOF也重现了比其前辈更具动态相关性的预测。

The relative stability of the singlet, triplet, and quintet spin states of Iron(II) porphyrin (FeP) represents a challenging problem for electronic structure methods. While it is currently accepted that the ground state is a triplet, multiconfigurational wavefunction-based methods predict a quintet, and density functional approximations vary between triplet and quintet states, leading to a prediction that highly depends on the features of the method employed. The recently proposed Global Natural Orbital Functional (GNOF) aims to provide a balanced treatment between static and dynamic correlation, and together with the previous Piris Natural Orbital Functionals (PNOFs), allowed us to explore the importance of each type of correlation in the stability order of the states of FeP with a method that conserves the spin of the system. It is noteworthy that GNOF correlates all electrons in all available orbitals for a given basis set; in the case of the FeP with a double zeta basis set as used in this work; this means that GNOF can properly correlate 186 electrons in 465 orbitals, significantly increasing the sizes of systems amenable to multiconfigurational treatment. Results show that PNOF5, PNOF7s and PNOF7 predict the quintet to have a lower energy than the triplet state; however, the addition of dynamic correlation via second-order Moller-Plesset corrections (NOF-MP2) turns the triplet state to be lower than the quintet state, a prediction also reproduced by GNOF that incorporates much more dynamic correlation than its predecessors.

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