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How deeply are core electrons perturbed when valence electrons are spin polarized? The case study of transition metal compounds
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2022-10-20 , DOI: 10.1002/jcc.27015
Fabien Pascale 1 , Klaus Doll 2 , Francesco Silvio Gentile 3 , Roberto Dovesi 4
Affiliation  

The ferromagnetic and antiferromagnetic wave functions of the KMnF3 perovskite have been evaluated quantum-mechanically by using an all electron approach and, for comparison, pseudopotentials on the transition metal and the fluorine ions. It is shown that the different number of α and β electrons in the d shell of Mn perturbs the inner shells, with shifts between the α and β eigenvalues that can be as large as 6 eV for the 3s level, and is far from negligible also for the 2s and 2p states. The valence electrons of F are polarized by the majority spin electrons of Mn, and in turn, spin polarize their 1s electrons. When a pseudopotential is used, such a spin polarization of the core functions of Mn and F can obviously not take place. The importance of such a spin polarization can be appreciated by comparing (i) the spin density at the Mn and F nuclear position, and then the Fermi contact constant, a crucial quantity for the hyperfine coupling, and (ii) the ferromagnetic–antiferromagnetic energy difference, when obtained with an all electron or a pseudopotential scheme, and exploring how the latter varies with pressure. This difference is as large as 50% of the all electron datum, and is mainly due to the rigid treatment of the F ion core. The effect of five different functionals on the core spin polarization is documented.

中文翻译:

当价电子自旋极化时,核心电子扰动的深度有多深?过渡金属化合物案例研究

KMnF 3的铁磁波函数和反铁磁波函数钙钛矿已经通过使用全电子方法进行了量子力学评估,并且为了比较,过渡金属和氟离子上的赝势。结果表明,Mn 的 d 壳层中不同数量的 α 和 β 电子扰动了内壳层,α 和 β 特征值之间的偏移对于 3s 能级可高达 6 eV,并且也远不能忽略对于 2s 和 2p 状态。F 的价电子被 Mn 的多数自旋电子极化,进而自旋极化它们的 1s 电子。当使用赝势时,Mn 和 F 的核心功能的这种自旋极化显然不会发生。通过比较 (i) Mn 和 F 核位置的自旋密度,然后是费米接触常数,可以理解这种自旋极化的重要性,超精细耦合的关键量,以及(ii)铁磁-反铁磁能差,当用全电子或赝势方案获得时,并探索后者如何随压力变化。这种差异高达全电子数据的50%,主要是由于F离子核的刚性处理所致。记录了五种不同功能对核心自旋极化的影响。
更新日期:2022-10-20
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