Spectroscopic determination of crystal field splittings in lanthanide double deckers
Spectroscopic determination of crystal field splittings in lanthanide double deckers
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DOI：
10.1039/c4sc00751d
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发表时间：
2014-01-01
期刊：
影响因子：
8.4
通讯作者：
van Slageren, J.
中科院分区：
文献类型：
--
作者：
Marx, R.;Moro, F.;van Slageren, J.
用远红外和非弹性中子散射光谱研究了典型的镧系单离子磁体及其配合物（NBu_4）（+）[LnPc（2）]（-）中心点2dmf（Ln = Dy，Ho，Er; dmf = N，N-二甲基甲酰胺）的晶场分裂。在每种情况下，我们已经发现了几个功能对应于直接晶体场跃迁内的地面多重峰。三个独立的峰的观察，在钬衍生物使我们能够获得晶体场分裂参数。此外，我们还进行了CASSCF计算。我们表明，利用CASSCF计算（用于状态的组成）和先进的光谱测量（用于准确确定能量）的相互作用是一种非常强大的方法来深入了解镧系元素单分子磁体的电子结构。
We have investigated the crystal field splitting in the archetypal lanthanide-based single-ion magnets and related complexes (NBu4)(+)[LnPc(2)](-)center dot 2dmf (Ln = Dy, Ho, Er; dmf = N, N-dimethylformamide) by means of far infrared and inelastic neutron scattering spectroscopies. In each case, we have found several features corresponding to direct crystal field transitions within the ground multiplet. The observation of three independent peaks in the holmium derivative enabled us to derive crystal field splitting parameters. In addition, we have carried out CASSCF calculations. We show that exploiting the interplay of CASSCF calculation (for the composition of the states) and advanced spectroscopic measurements (for accurate determination of the energies) is a very powerful approach to gain insight into the electronic structure of lanthanide-based single-molecule magnets.