通过红外光谱技术探讨了高氯酸锂甲醇溶液中离子与溶剂、离子与离子之间的相互作用。红外光谱分析结果表明:锂离子与溶剂发生了相互作用导致甲醇分子的O-H伸缩振动区蓝移,ClO-4的特征谱带的变化表明了溶液中存在离子缔合。根据密度泛函理论,对不同溶剂化数的配合物结构和两种离子对形式进行优化及热力学性质的计算。

Interactions between ions and solvent as well as between ions themselves in a methanol solution of lithium perchlorate were studied by IR spectrometry. As shown by the experimental results, the spectral change of solvent molecule, i.e., the molecule of CH3OH, was due to the interaction between the Li+ ion and CH3OH molecule leading to hypsochromic shift of stretching vibration of O-H group, and it was deduced that the hydrogen bonds between CH3OH molecules were destroyed by the solvation of Li+ ion. Ion association between Li+ and ClO-4 to form (Li+ClO-4) ion pair and its dimer (Li+ClO-4)2 was proved by the change of characteristic bands of ClO-4 ion. Based on the density-functional theory, optimization of structures of the coordination complex ［Li(CH3OH)n］+ with different solvation numbers from 1 to 4 and the ion association complexes of (Li+ClO-4) and (Li+ClO-4)2 as well as the thermodynamic parameters were calculated.