高氯酸根及其离子对光谱指认的量子化学研究

利用红外和拉曼光谱研究了不同浓度下高氯酸锂在N,N-二甲基甲酰胺、乙腈、四氢呋喃、丙酮、二甲亚砜、乙酸甲酯等有机溶剂中的缔合情况,分析了高氯酸根v1谱带的变化,指认了溶液中光谱自由离子、直接接触离子对和离子对二聚体.使用量子化学方法计算了不同结构直接接触离子对和离子对二聚体的稳定构型和光谱行为,并和实验值进行了比较,考察了溶剂化模型、溶剂分子对直接接触离子对或离子对二聚体结构的影响,探讨了量子化学方法指认离子对的可能性和正确性.

Ab initio calculations of vibrational frequencies and structures of ion pairs of perchlorate

Ion association of solutions of lithium perchlorate in N,N-dimethylformamide, acetonitrile, tetrahydrofuran, acetone, methyl acetate and other organic solvents have been investigated by infrared and Raman spectroscopy, respectively. The spectroscopically free ion, contact ion pair and dimer are fingerprint by the curve fitting of upsilon1 band of. The most stable geometries of contact ion pairs and dimmer, and the vibrational frequencies were optimized and calculated using the ab initio methods. The comparison between calculated and experimental data of band position was made. Effect of solvation mode and solvent molecule on the vibrational frequencies of ion pairs was also indicated.