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：

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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。