Nakano Hiroshi, Noguchi Junki, Mochida Tomoyuki, Sato Hirofumi
§Department of Chemistry, Kobe University, Rokkodai, Nada, Kobe 657-8501, Japan.
J Phys Chem A. 2015 May 28;119(21):5181-8. doi: 10.1021/jp509859f. Epub 2014 Dec 17.
The solvation effects on the electronic structures and magnetic properties were computed for a series of ferrocenium cations in the ferrocenium-based ionic liquids using RISM-SCF-SEDD calculations coupled with CASSCF. The spin-orbit coupling was calculated to get insight into the spin anisotropy. The values were on the order of 100 cm(-1), exhibiting strong spin anisotropy parallel to the angular momentum. The computed results show that the magnetic properties of the ferrocenium cations are similar both in the isolated state and in ionic liquids. We also carried out molecular dynamics and RISM calculations to investigate the liquid structures. The radial and spatial distribution functions around the cations indicate that the cations are surrounded by about seven TFSA anions above and below the cyclopentadienyl rings and from the side of the ferrocenium cations. The nearest-neighbor cations exist in the oblique directions. The introduction of a butyl group to the ring disturbs the solvation structures, and butyl groups in different cations tend to attract each other like those observed in alkylimidazolium ionic liquids.
使用RISM-SCF-SEDD计算结合CASSCF，对基于二茂铁鎓的离子液体中的一系列二茂铁鎓阳离子的溶剂化效应及其电子结构和磁性进行了计算。计算了自旋轨道耦合以深入了解自旋各向异性。其值约为100 cm⁻¹，表现出与角动量平行的强自旋各向异性。计算结果表明，二茂铁鎓阳离子在孤立状态和离子液体中的磁性相似。我们还进行了分子动力学和RISM计算以研究液体结构。阳离子周围的径向和空间分布函数表明，阳离子在环戊二烯基环的上方和下方以及从二茂铁鎓阳离子的侧面被大约七个TFSA阴离子包围。最近邻阳离子以倾斜方向存在。向环中引入丁基会扰乱溶剂化结构，并且不同阳离子中的丁基倾向于像在烷基咪唑鎓离子液体中观察到的那样相互吸引。
