Spectrum And Theoretical Study On The Salvation Effect Of More Electron Elements

Solvation phenomena has been found a variety of applications, such as physical、 chemical, and biological processes, to unveil the nature of ion solvation, tremendous scientific efforts have been paid for decades, Raman、IR、NMR spectroscopy and X-ray diffraction methods have been applied in studying the solvent structures and properties of ions. However many fundamental questions remain not understood. On the other hand, rare earth coordinations have been increasingly found that their extensive applications in modern science and technology, owing to the particularly chemical and physical properties. On quantum chemistry calculation, their open 4f shell of rare earth would make it difficult in structure optimization, which mainly due to their large number of electrons and relativistic effects. On the basis of predecessor’s research works and related literatures information, the study aim mainly focus on ions solvation phenomenon by using improved quantum chemistry calculation methods and molecular spectroscopy. The main contents of the present work are as follows:Part one B3LYP and CCSD methods have been applied in the struture calculation of [Cl(H20)n]-(n=1-4). Comparing the results with MP2 which has been reported in the literature, B3LYP function method is found rather reasonable. Then, K+ and Cl-, which have a comparable ionic radius, not in charge, have been investigated in water using density functional theory (DFT) at the B3LYP/6-311++G(2d,2p). The characterizations of the [K(H2O)n]+、[Cl(H2O)n]- and [KCl(H2O)n](n=1-5)clusters, which including optimal structures, structural parameters, binding energies, formation energy, and energy gap, etc., have been calculated to determine their magic number structures. Finally, by the analysis of the probable reasons of the magic stable clusters, the mechanism of Cl" in solution could been explained.Part two In order to evaluate the effect of TPSSTPSS density functional on the lanthanide complexes deeply, the popular eight DFT functionals have been applied in the evaluation with our proposed functional method. The results have showed TPSSTPSS density functional with minor errors. Besides, solvation structures of La3+ in water have been calculated using the method first, which indicated that the result of optimized structures in gas phase result is near to that in liquid. By taking the high computational cost and necessary calculation accuracy into consideration, the optimized clusters structures in liquid could be instead of those in gas, which is more effective and in agreement with the references too. Finally [La(C2H5OH)n]3+ (n=3-7) cluster structures in the first solvation shell have been calculated including optimal structures, structural parameters, thermodynamic constants and theoretical NMR by using improved TPSSTPSS level, and 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. Both fluorescence and NMR experiment spetrum have been employed to verify above proposed method, the results have demonstrated that the proposed method is good at calculating of lanthanum ion with more electrons in ethanol soluation. The method should provide an effectively exploratory method on short-range molecular interactions in solution.Part three The molecular geometries of Europium chloride solvation in organic solvents ethanol have been explored and ascribed by using TPSSTPSS density functional. Through the optimization of the probable clusters in solution based on eliminating the false frequency, their structural parameters and thermodynamic constants have been obtained, and the probable magic number structures are analysised too. Finally, both fluorescence and ramam spectrometry experiments have been employed to verify the theoretical calculation results of Europium ion in ethanol, the effect of 4f shell orbital electrons on its spectrum and the changes have also been explained reasonably.