Ultra-Broadband Dielectric and Optical Kerr-Effect Study of the Ionic Liquids Ethyl and Propylammonium Nitrate.

Ultra-Broadband Dielectric and Optical Kerr-Effect Study of the Ionic Liquids Ethyl and Propylammonium Nitrate.
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离子液体乙基和丙基硝酸铵的超宽带介电和光学克尔效应研究。

DOI:
10.1021/jp502935t
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发表时间:
2015
期刊:
The journal of physical chemistry. B
影响因子:
--
通讯作者:
Sonnleitner T
Sonnleitner T
中科院分区:
--
文献类型:
--
作者:
Sonnleitner T

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在200 MHz ~ 10 THz的频率范围内,测量了典型质子离子液体硝酸乙基铵和硝酸丙基铵(EAN和PAN)的介电弛豫(DR)和光学克尔效应(OKE)谱,温度(大部分)在5 ~ 65 °C之间。低频α弛豫与阳离子(DR)和阴离子(OKE)以及任何存在的簇的协同弛豫相关,分析表明EAN中的离子重取向与粘度无关,并且通过涉及大角度跳跃而不是旋转扩散的协同弛豫发生。对DR和OKE光谱的高频部分的详细考虑表明,观察到的强度是重叠和可能耦合模式的复杂组合。除了先前确定的分子间H-键振动,有显着的贡献,从阳离子和阴离子的振动。本分配被证明是一致的同位素位移观察到的氘代EAN。
Dielectric relaxation (DR) and optical Kerr-effect (OKE) spectra of the archetypal protic ionic liquids ethyl- and propylammonium nitrate (EAN and PAN) have been measured over an unusually large frequency range from 200 MHz to 10 THz at temperatures (mostly) between 5 and 65 °C. Analysis of the low-frequency α-relaxation, associated with the cooperative relaxations of the cations (DR) and anions (OKE) and any clusters present, indicated that ion reorientation in EAN is decoupled from viscosity and occurs via cooperative relaxation involving large-angle jumps rather than rotational diffusion. Detailed consideration of the high-frequency parts of the DR and OKE spectra showed that the observed intensities were a complex combination of overlapping and possibly coupled modes. In addition to previously identified intermolecular H-bond vibrations, there are significant contributions from the librations of the cations and anions. The present assignments were shown to be consistent with the isotopic shifts observed for deuterated EAN.
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