论文标题
[lnpc $ _2 $] $^0 $：通过AB INLIOO捕获的多次参考计算捕获的灯笼中激进的磁耦合$^0 $：
Lanthanide-radical magnetic coupling in [LnPc$_2$]$^0$: Competing exchange mechanisms captured via ab initio multi-reference calculations
论文作者
论文摘要
我们对[lnpc $ _2 $] $^0 $（ln = tb，dy，ho和er）中分子内交换耦合的计算研究进行了调查。在[LNPC $ _2 $] $^0 $上，在[LNPC $ _2 $^0 $上以及较小的模型化合物[lnpz $ _2 $^0 $^0 $^0 $^0 $^0 $^0 $上执行了一系列一系列的主载多构算/多参考完整/限制的活跃空间自动式磁场计算（CASSCF/RASSCF），包括非扰动旋转旋转 - 轨道耦合。我们发现，交换耦合机制受对称的限制，但也取决于PC $ _2 $ figands $π$ - $π^*$激发触发的自旋极化效应。计算出的交换分组很小，最多等同于几个CM $^{ - 1} $，与以前的文献报道不同意强烈的反铁磁耦合，但与[TBPC $ _2 $ _2 $] $^0 $的最新EPR实验非常吻合。此外，发现耦合强度从[tbpc $ _2 $] $^0 $降低到[erpc $ _2 $] $^0 $，在灯笼地面（Hund's Rules）Russell-saunders术语中，不成对的电子旋转数量减少。
We present a computational investigation of the intramolecular exchange coupling in [LnPc$_2$]$^0$ (Ln = Tb, Dy, Ho, and Er) between the Ln$^{3+}$ 4f electrons and the spin-1/2 radical on the phthalocyanine ligands. A series of ab initio multi-configurational/multi-reference Complete/Restricted Active Space Self-Consistent-Field calculations (CASSCF/RASSCF), including non-perturbative spin--orbit coupling, were performed on [LnPc$_2$]$^0$ and on the smaller model compound [LnPz$_2$]$^0$. We find that the exchange coupling mechanisms are restricted by symmetry, but also dependent on the spin polarization effect triggered by the Pc$_2$ ligands $π$--$π^*$ excitations. The calculated exchange splittings are small, amounting to at most a few cm$^{-1}$, in disagreement with previous literature reports of strong antiferromagnetic coupling, but in good agreement with recent EPR experiments on [TbPc$_2$]$^0$. Furthermore, the coupling strength is found to decrease from [TbPc$_2$]$^0$ to [ErPc$_2$]$^0$, with decreasing number of unpaired electron spins in the lanthanide ground (Hund's rule) Russell--Saunders term.
