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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Solvation of propylene oxide in water: Vibrational circular dichroism, optical rotation, and computer simulation studies
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Solvation of propylene oxide in water: Vibrational circular dichroism, optical rotation, and computer simulation studies

机译：环氧丙烷在水中的溶解：振动圆二色性，旋光性和计算机模拟研究

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摘要

The solvation of propylene oxide (PO) in water has been studied using vibrational circular dichroisim (VCD) spectroscopy, optical rotation dispersion (ORD) spectroscopy, molecular dynamics simulations, and ab initio calculations. VCD and ORD measurements were carried out for PO as neat liquid, in CCl4, and in water solutions. The classical molecular dynamics simulations were carried out for the PO + water binary mixtures at different concentrations, and the solvation information was derived from the radial distribution functions obtained in the simulations. The total number of water molecules within the closest vicinity of PO was predicted to be about 3. The geometry optimizations, vibrational frequencies, and VCD intensities were evaluated for the PO monomer and the PO-(H2O)(n) clusters with n = 1-3, using density functional theory calculations at the B3LYP/aug-cc-pVTZ level of theory. The chirality transfer VCD feature, which is a direct result of the explicit H-bonding between water and the chiral PO solute, was detected experimentally at the water bending band region. This feature exhibits high sensitivity to the solvation structure around PO. Comparison of the calculated and experimental chirality transfer features leads to the conclusion that the PO-water binary complex is the dominating species in aqueous solution at room temperature and the anti conformation, where water is on the opposite side of the oxirane ring of the PO methyl group, is preferred over the syn one. This Conclusion is also supported by the complementary ORD studies. Possible contributions from the ternary and quaternary PO-water complexes are also discussed.
机译：已经使用振动圆二色谱（VCD）光谱，旋光色散（ORD）光谱，分子动力学模拟和从头算来研究环氧丙烷（PO）在水中的溶剂化。对于纯净的PO，CCl4和水溶液，进行了VCD和ORD测量。对不同浓度的PO +水二元混合物进行了经典的分子动力学模拟，并且溶剂化信息是从模拟中获得的径向分布函数得出的。预测PO附近最接近的水分子总数约为3。对PO单体和n = 1的PO-（H2O）（n）团簇的几何优化，振动频率和VCD强度进行了评估。 -3，使用B3LYP / aug-cc-pVTZ理论级别的密度泛函理论计算。在水弯曲带区域通过实验检测到手性转移VCD特征，这是水与手性PO溶质之间显式H键的直接结果。该特征对PO周围的溶剂化结构表现出高敏感性。计算和实验的手性转移特征的比较得出以下结论：PO-水二元络合物是室温下水溶液中的主要物种和反构象，其中水在PO甲基环氧乙烷环的相反侧组，比syn组优先。补充ORD研究也支持该结论。还讨论了三元和四元PO-水络合物的可能贡献。

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