Density Functional Study of the Conformations and Vibrations of 1,2-Dimethoxyethane
Density Functional Study of the Conformations and Vibrations of 1,2-Dimethoxyethane
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1,2-二甲氧基乙烷构象和振动的密度泛函研究
DOI：
10.1021/jp9800766
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发表时间：
1998
影响因子：
2.9
通讯作者：
H. Matsuura
中科院分区：
文献类型：
--
作者：
Hiroshi Yoshida and;H. Matsuura
用密度泛函理论（DFT）研究了1，2-二甲氧基乙烷（DME）的构象和振动，并与分子轨道（MO）方法进行了比较。使用6- 31 G * 基组的计算通过五种DFT方法（BVWN、BP 86、BLYP、B3 PW 91和B3 LYP）和两种MO方法（HF和MP2）进行。与其他方法相比，采用B3交换泛函的DFT方法能更好地预测构象异构体的能量。用密度泛函和分子轨道方法计算的振动波数解释了正常和全氘代DME分子的拉曼和红外光谱。结果表明，DME在固态时的构象为TGT，在液态时的构象为TGT、TTT、TGG '和TTG。本计算进一步表明，TGG和GGG构象也存在于液体状态。无标度的计算波数与实验波数之比的分布随温度的升高而变窄。
The conformations and vibrations of 1,2-dimethoxyethane (DME) have been studied by density functional theory (DFT) in comparison with the molecular orbital (MO) methods. The calculations using the 6-31G* basis set were performed by five DFT methods (BVWN, BP86, BLYP, B3PW91, and B3LYP) and two MO methods (HF and MP2). The energies of conformers were better predicted by the DFT methods using the B3 exchange functional than other methods. The vibrational wavenumbers calculated by the DFT and MO methods explained, after correcting with uniform scaling, the observed Raman and infrared spectra of the normal and perdeuterated species of DME. It was confirmed that the conformer of DME present in the solid state is TGT, and the conformers in the liquid state are TGT, TTT, TGG‘, and TTG. The present calculations further indicated that the TGG and GGG conformers are also present in the liquid state. The distributions of the ratio of the unscaled calculated wavenumber to the experimental wavenumber are narrower with...