Abstract

Electronic structures of ionic liquids formed by 1-buthyl-3-alkylimidazolium ion [C n mim] + ( n = 4 and 8) with various inorganic and organic anions have been investigated by ultraviolet photoemission, X-ray photoemission, inverse photoemission and soft X-ray emission spectroscopies (SXES). The comparison of the calculated density of states with the observed spectra revealed that the molecular orbital energies of these ionic liquids are significantly affected by the electrostatic Madelung potential among the ions. The SXES results clearly show that the both highest occupied and lowest unoccupied states of [C 4mim] +PF 6 − are derived from the cation as a result of strong Madelung potential. On the other hand, the SXES results show the valence electronic structures of ionic liquids with larger anion molecules, [C n mim] +Tf 2N − and [C n mim] +OTf − are contributed from the both cation and anion.

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