| 吴晓静,于亚鹏,蒋卫国,权俊杰,王小英.化学通报,2015,78(1):49-54. |
| La(Ⅲ)-乙醇溶液微团簇理论和光谱研究 |
| Theory and Experimental Dependence of Molecular Geometries of La(Ⅲ)Solvation in Ethanol |
| 投稿时间：2014-04-01 修订日期：2014-05-21 |
| DOI： |
| 中文关键词: 密度泛函 赝势基组 溶剂化数 屏蔽效应 |
| 英文关键词:DFT, pseudopotential basis, solvation number , shielding effect |
| 基金项目: |
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| 摘要点击次数: 2749 |
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| 中文摘要: |
| 利用分子光谱和基于密度泛函理论的第一性原理研究La3 /乙醇溶液微团簇构型。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。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,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,化学位移向高场位置移动,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。 |
| 英文摘要: |
| The molecular geometries of lanthanum chloride solvation in ethanol were calculated and ascribed by using density functional theory(DFT) and spectroscopy. In this study, the improved TPSSTPSS level based on the first-principle method, combined with Def2-SV(P) for lanthanide metal while using all-electron basis sets(6-31G (d,p)) for C、H、O mixed basis set, has been mainly applied in the interaction of lanthanum ion with ethanol. Solvation structures of La3 in water were calculated using proposed calculation method first, the results were in agreement with the references. Then the fluorescence spectrometry and NMR experiment have been used to verify the theoretical calculation results of lanthanum ion in ethanol, which illustrated that the most stable cluster structure is (La(C2H5OH)6)3 . Moreover lanthanum ion increased fluorescence intensity significantly. The cluster configuration is more stable in high concentration, with the increase of solvation number, the O--H distances increased and the protons near lanthanum ion produced powerful shielding effect which induced the position of chemical shift to high field, the total absolute error was least when n=6, these also in conformity with theoretical calculations . |
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