Theoretical investigation of the interaction between monohalogenated ethenes and hydrogen peroxide

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• 作者：Pham Ngoc Diep ; Hue Minh Thi Nguyen ; Tran Thanh Hue ; Thé ; rè ; se Zeegers-Huyskens
• 关键词：Monohalogenated ethers– ; hydrogen peroxide complexes ; Ab initio calculations ; Blue shifts of the CH stretching vibrations
• 刊名：Journal of Molecular Structure
• 出版年：2010
• 出版时间：15 July 2010
• 年：2010
• 卷：976
• 期：1-3
• 页码：73-80
• 全文大小：791 K

文摘

The complexes between monohalogenated ethenes CH₂CHX (X = F, Cl, Br) and hydrogen peroxide (HP) have been studied theoretically at the MP2/6-311++G(3df,2p) level. The calculations include the optimization of the geometries, the vibrational frequencies and IR intensities of the ν(OH) and ν(CH) vibrations along with a natural bond orbital (NBO) analysis. The most stable complexes having binding energies between 7 and 12 kJ mol⁻¹ have a cyclic structure characterized by OH…X and CH…O hydrogen bonds. Less stable complexes having binding energies of 6 kJ mol⁻¹ are stabilized by two CH…O hydrogen bonds. The complexes are slightly more stable than the corresponding CH₂CHX · H₂O complexes, showing the predominance of the proton donor in determining the hydrogen bond energies. The variations of the NBO charges on the two partners are discussed. Blue shifts are predicted for the ν(CH) vibrations of the CH…O bonds and red shifts for the ν(OH) vibrations in the OH…X bonds. The data are discussed as a function of the change in hybridization of the C atom along with the occupation of the σ*CH) orbitals. Intramolecular and intermolecular hyperconjugations are discussed as well. The geometric data and NBO parameters suggest that the strength of the CH…O hydrogen bonds are ordered according CH₂CHF < CH₂CHCl < CH₂CHBr. An inverse order is found for the OH…X hydrogen bonds.