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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Investigation of the Interaction between Fluorinated Dimethyl Ethers(nF ) 1-5) and Water: Role of the Acidity and Basicity on the Competition between OH…O and CH…O Hydrogen Bonds
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Theoretical Investigation of the Interaction between Fluorinated Dimethyl Ethers(nF ) 1-5) and Water: Role of the Acidity and Basicity on the Competition between OH…O and CH…O Hydrogen Bonds

机译：氟化二甲醚（nF）1-5）与水相互作用的理论研究：酸度和碱度对OH…O和CH…O氢键竞争的作用

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摘要

Theoretical calculations have been carried out using ab initio MP2 and B3LYP density functional methods to investigate the interaction between fluorinated dimethyl ethers (nF ) 1-5) and water. Depending on the number of F atoms implanted on the dimethyl ethers, linear structures stabilized by intermolecular OwHw…O or CH…Ow hydrogen bonds or closed structures involving both hydrogen bonds are formed. Binding energies of the hydrogen-bonded complexes range between 4 and 12 kJ mol-1. Blue shifts of the CH stretching vibrations are predicted even in the absence of a direct CH…O interaction. The red shifts of the OH stretching vibrations of water in the open and closed structures are analyzed as well. The natural bond orbital analysis includes the σ*(OwHw) and σ*(CH) occupation, the hybridization of the C atom, the atomic charges, and the intra- and intermolecular hyperconjugation energies. These parameters are discussed as a function of the proton affinity(PA) of the O atom and the deprotonation enthalpy (DPE) of the CH bonds of the fluorinated ethers calculated in a previous work.16 Our results show that the effective PA in determining the intermolecular O f σ*(OwHw) hyperconjugation energies decreases with increasing acidity of the CH bond. In turn, the effective acidity of the CH bond in determining the intermolecular Ow f σ*(CH) hyperconjugation energies decreases with increasing basicity of the O atom.
机译：已经使用从头开始的MP2和B3LYP密度泛函方法进行了理论计算，以研究氟化二甲醚（nF 1-5）与水之间的相互作用。取决于注入二甲醚上的F原子的数量，形成由分子间OwHw…O或CH…Ow氢键稳定的线性结构或涉及两个氢键的封闭结构。氢键配合物的结合能在4至12 kJ mol-1之间。即使没有直接的CH…O相互作用，也可以预测CH拉伸振动的蓝移。还分析了开放结构和封闭结构中水的OH拉伸振动的红移。自然键轨道分析包括σ*（OwHw）和σ*（CH）占据，C原子的杂化，原子电荷以及分子内和分子间的超共轭能。讨论了这些参数是O原子的质子亲和力（PA）和氟化醚的CH键的去质子化焓（DPE）的函数，该结果在先前的工作中进行了计算。16我们的结果表明，确定PA的有效PA分子间的O fσ*（OwHw）超共轭能随着CH键酸度的增加而降低。反过来，随着O原子碱性的增加，确定分子间Ow fσ*（CH）超共轭能时CH键的有效酸度降低。

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