Vibrational and theoretical study of the complexation of LiPF₆ and LiClO₄ by di(ethylene glycol) dimethyl ether

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• 作者：Grondin ; Joseph ; Ducasse ; Laurent ; Bruneel ; Jean-Luc ; Servant ; Laurent ; Lassè ; gues ; Jean-Claude
• 关键词：Lithium complexes ; Diglyme ; Infrared ; Raman ; Ion-pairing ; 78.30.&minus ; j ; 33.20.Tp ; 33.40.Mr ; 61.20.Qg
• 刊名：Solid State Ionics
• 出版年：2004
• 出版时间：January 30, 2004
• 年：2004
• 卷：166
• 期：3-4
• 页码：441-452
• 全文大小：729 K

文摘

Solid [(diglyme)₂Li⁺]PF₆⁻ and [(diglyme)₂Li⁺]ClO₄⁻ salts melting at 132 and 66 °C, respectively, have been isolated. They involve two diglyme molecules wrapping the six-coordinated cation and a “spectroscopically free” anion in a similar local structure of complexation as in the P(EO)₆,LiPF₆ and P(EO)₆,LiClO₄ systems. The structures and vibrational assignments of the [(diglyme)₂Li⁺]X⁻ salts have been established by comparison with the corresponding IR and Raman spectra of liquid and solid diglyme and by using ab initio calculations. In particular, the atomic motions involved in the so-called “rattling”, D-LAM or “breathing” modes have been described in terms of a distorted octahedral cage of oxygen coordinating the lithium. Various (diglyme)_n,LiClO₄ samples (n