Theoretical
Studies on the Electronic States and Liquid Structures of Ferrocenium-Based
Ionic Liquids
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Abstract
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<sup>–1</sup>, 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