二甲氧基乙烷
化学
四氢呋喃
溶剂化
二聚体
电解质
密度泛函理论
从头算
从头算量子化学方法
拉曼光谱
单体
溶剂
计算化学
物理化学
分子
有机化学
物理
电极
光学
聚合物
作者
Olivia B.A. Quintanilha,Wagner A. Alves,Andrzej Eilmes
标识
DOI:10.1016/j.molliq.2023.123927
摘要
The 1:1 MgCl2:AlCl3 (MACC)-based electrolyte was spectroscopically investigated for the first time in the presence of an equimolal 1,2-dimethoxyethane (DME):tetrahydrofuran (THF) mixture. Composition-dependent Raman spectra suggested that the new bands at 896 and 883 cm−1 correspond to the mixed νCO and νCC vibrations of both ethers coordinated to Mg(II) ions. A signal at 219 cm−1, which is assigned to the νMgCl vibration, was only observed for the highest acid-base pair content, in contrast to the behavior exhibited in the acyclic ether alone. Density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations revealed that the [MgCl(DME)(THF)3]+ and [MgCl(DME)2THF]+ monomers may be associated to the experimental bands observed at the solvent region, thus being predicted at 867 and 858 cm−1, respectively. The [Mg2(μ-Cl)2(DME)4]2+ dimer has a theoretical band at 216 cm−1, which is related to the experimentally observed signal at the low wavenumber region. The preferential solvation effect is discussed in detail for the studied solvates.
科研通智能强力驱动
Strongly Powered by AbleSci AI