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利用分子光谱和基于密度泛函理论的第一性原理,采用改进的TPSSTPSS泛函方法对C、H、O原子用6-31G基组并添加极化和弥散函数,对La原子选用Def2-SV(P)赝势基组,研究La3+/乙醇溶液微团簇构型。优化计算La3+在水溶液中的溶剂化结构,得出气相中的优化结果可以近似代替液相结果的结论;理论优化计算La3+/乙醇溶液可能存在的结构构型的结果表明,溶剂化数n=6时结构最稳定。采用荧光光谱和核磁共振实验对结果进行了验证,表明La3+的加入使荧光强度显著增强,在高浓度时生成的团簇构型比较稳定,且随着溶剂化数目的增加,O—H键长增大,La3+使其附近的质子产生强大的屏蔽效应,化学位移向高场移动,溶剂化数n=6时绝对误差最小,最稳定,与理论计算结论相吻合。
Using molecular spectroscopy and first-principles based on density functional theory, a modified TPSSTPSS functional approach was used to polarize and diffuse the C, H, O atoms with a 6-31G basis set and the Def2-SV (P) pseudopotential base group to study the micro-cluster configuration of La3 + / ethanol solution. The solvation structure of La3 + in aqueous solution was optimized and the conclusion was obtained that the optimization results in the gas phase could replace the results of the liquid phase. The theoretical optimization of the possible configuration of La3 + / ethanol solution showed that the solvation number was n = 6 When the structure is the most stable. The results of fluorescence spectroscopy and nuclear magnetic resonance tests confirmed that the addition of La3 + significantly enhanced the fluorescence intensity of the cluster formed at high concentrations of relatively stable, and with increasing the number of solvation, O-H bond length Increases, and La3 + has strong shielding effect on the protons nearby. The chemical shift moves to the high field. When the solvation number is n = 6, the absolute error is the smallest and the most stable, which agrees well with the theoretical calculation.