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Intermolecular Interactions in Li + ‐glyme and Li + ‐glyme–TFSA − Complexes: Relationship with Physicochemical Properties of [Li(glyme)][TFSA] Ionic Liquids
Author(s) -
Tsuzuki Seiji,
Shinoda Wataru,
Seki Shiro,
Umebayashi Yasuhiro,
Yoshida Kazuki,
Dokko Kaoru,
Watanabe Masayoshi
Publication year - 2013
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201200843
Subject(s) - chemistry , binding energy , atom (system on chip) , ion , lithium (medication) , crystallography , atomic physics , organic chemistry , medicine , physics , computer science , embedded system , endocrinology
The stabilization energies (Δ E form ) calculated for the formation of the Li + complexes with mono‐, di‐ tri‐ and tetra‐glyme (G1, G2, G3 and G4) at the MP2/6‐311G** level were −61.0, −79.5, −95.6 and −107.7 kcal mol −1 , respectively. The electrostatic and induction interactions are the major sources of the attraction in the complexes. Although the Δ E form increases by the increase of the number of the O⋅⋅⋅Li contact, the Δ E form per oxygen atom decreases. The negative charge on the oxygen atom that has contact with the Li + weakens the attractive electrostatic and induction interactions of other oxygen atoms with the Li + . The binding energies calculated for the [Li(glyme)] + complexes with TFSA − anion (glyme=G1, G2, G3, and G4) were −106.5, −93.7, −82.8, and −70.0 kcal mol −1 , respectively. The binding energies for the complexes are significantly smaller than that for the Li + with the TFSA − anion. The binding energy decreases by the increase of the glyme chain length. The weak attraction between the [Li(glyme)] + complex (glyme=G3 and G4) and TFSA − anion is one of the causes of the fast diffusion of the [Li(glyme)] + complex in the mixture of the glyme and the Li salt in spite of the large size of the [Li(glyme)] + complex. The HOMO energy level of glyme in the [Li(glyme)] + complex is significantly lower than that of isolated glyme, which shows that the interaction of the Li + with the oxygen atoms of glyme increases the oxidative stability of the glyme.