MnCl2/DMSO溶液的拉曼光谱和理论计算

doi:10.7503/cjcu20170390

摘要/Abstract

摘要：

利用拉曼光谱研究了不同温度和浓度MnCl₂/DMSO溶液体系离子的溶剂化作用, 结果表明, 在0~0.8 mol/L浓度范围内, 随着浓度增加, Mn²⁺与DMSO的相互作用逐渐增强, S=O伸缩振动峰向低波数移动, S=O双键减弱; C—S伸缩振动峰向高波数移动, C—S键增强. 温度升高, S=O双键和C—S键伸缩振动峰均向相反的方向移动, 溶剂化作用减弱. 56 ℃以上, 单体DMSO迅速增加, 与Mn²⁺溶剂化作用的DMSO迅速减少, 二聚体DMSO减少缓慢, 温度对溶剂化作用的影响大于溶剂自身的缔合. 利用密度泛函理论对可能存在的溶剂化构型[Mn(DMSO)_n]²⁺进行了优化、热力学性质及理论拉曼光谱计算, 从理论上证实了Mn²⁺与DMSO存在相互作用, 导致DMSO的S=O键拉伸和C—S键收缩, 与实验光谱结果一致.

关键词: 氯化锰/二甲基亚砜溶液, 拉曼光谱, 溶剂化作用, 溶剂化构型

Abstract:

The ion solvation of MnCl₂/DMSO solutions was investigated by Raman spectra in different concentrations and temperatures. The results indicated that Mn²⁺ coordinated with DMSO molecules in the form of ions in the solutions, and the interaction gradually strengthened with the increase of concentrations between 0—0.8 mol/L. With the solvation of Mn²⁺ and DMSO molecules interaction increasing, S=O double peaks moved to low wave number, so S=O double bond weakened; C—S stretching vibration peak moved to high wave number, so C—S bond strengthened. Rising temperature, S=O double bond and C—S bond vibration peaks moved to the opposite direction, and the solvation effects gradually weaken. Above 56 ℃, monomer DMSO molecules rapidly increasing, DMSO molecules in the solvation sphere of the manganese cation rapidly reducing, dimer DMSO molecules slowly reducing, that illustrated that temperature had a greater influence on solvation effects than the association of solvent itself. Moreover the optimized possible solvation configuration [Mn(DMSO)_n]²⁺, thermodynamic properties, and the theory of Raman spectra were calculated by density functional theory. The solvation of Mn²⁺ and DMSO molecules was confirmed by theory, which resulted in stretching of S=O bond and the contraction of C—S bond, consisting with the results of the experimental spectrum.

Key words: MnCl₂/DMSO solution, Raman spectrum, Solvation, Solvation configuration

TrendMD:

吴晓静, 刘阿钻. MnCl₂/DMSO溶液的拉曼光谱和理论计算. 高等学校化学学报, 2017, 38(12): 2220.

WU Xiaojing, LIU Azuan. Studies of Raman Spectra and Theoretical Calculation of MnCl₂/DMSO Solution. Chem. J. Chinese Universities, 2017, 38(12): 2220.

图/表 11

Fig.1 Raman spectra of pure DMSO and different concentrations of MnCl2 / DMSO solutions (A) S=O stretching vibration; (B) C—S stretching vibration.

Fig.2 S=O stretching vibration bands of pure DMSO(A) and 1.0 mol/L MnCl2/DMSO solution(B)

Fig.3 Spectra changes of C—S stretching vibration area in 0.2 mol/L(A) and 1.0 mol/L(B) MnCl2/DMSO solutions

Fig.4 Linear diagrams of various type of DMSO molecules with different concentrationsa. Monomer; b. dimer; c. coordinate with Mn2+.

Fig.5 Raman spectra of different temperatures in 0.8 mol/L MnCl2/DMSO solution (A) SO stretching vibration; (B) C—S stretching vibration.

Fig.6 S=O stretching vibration bands of 0.8 mol/L MnCl2/DMSO solutionat 24 ℃(a) and 88 ℃(b)

Fig.7 Spectra changes of C—S stretching vibration area in 0.8 mol/L MnCl2/DMSO solution at 24 ℃(A) and 88 ℃(B)

Fig.8 Linear diagrams of various type of DMSO molecules at different temperatures a. Monomer; b. dimer; c. coordinate with Mn2+.

Table 1 Bond parameters and the changes of Gibbs free energy(ΔG) of different configurations

Species	d(S=O)/nm	d(C—S)/nm	ΔG/(kJ·mol^-1)
DMSO	0.1511	0.1837
(DMSO)₂	0.1522	0.1831
[Mn(DMSO)]²⁺	0.1667	0.1813	-765.8
[Mn(DMSO)₂]²⁺	0.1606	0.1811	-469.9
[Mn(DMSO)₃]²⁺	0.1593	0.1812	-239.1
[Mn(DMSO)₄]²⁺	0.1584	0.1813	-187.7
[Mn(DMSO)₅]²⁺	0.1570	0.1817	-42.6
[Mn(DMSO)₆]²⁺	0.1561	0.1818	-51.5

Fig.9 B3LYP optimized the stable structures of (DMSO)2 and [Mn(DMSO)n]2+(n=1—6)

Fig.10 Theory and experiment spectra of C—S stretching vibration(A) The cumulative peak of DMSO and (DMSO)2; (B)experimental spectra of pure DMSO; (C) the cumulative peak of [Mn(DMSO)n]2+(n=1—6); (D) experimental spectra of 1.0 mol/L MnCl2/DMSO.

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MnCl₂/DMSO溶液的拉曼光谱和理论计算

Studies of Raman Spectra and Theoretical Calculation of MnCl₂/DMSO Solution

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