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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Study of the Interaction between Methyl Fluoride,Methyl Chloride,and Methyl Bromide with Hydrogen Peroxide
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Theoretical Study of the Interaction between Methyl Fluoride,Methyl Chloride,and Methyl Bromide with Hydrogen Peroxide

机译：氟化氢，氯甲烷和溴甲烷与过氧化氢相互作用的理论研究

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摘要

MP2/6-31+G(d,p)calculations are used to analyze the interaction between CH_3X(X=F,Cl,or Br)and hydrogen peroxide(HP).Two stable structures,A and B,are found on each potential energy surface.The A complexes are characterized by a six-membered structure and the B complexes,having a lower stability,by a five-membered structure.In both complexes,the molecules are held together by both OH…X and CHI…O hydrogen bonds.The binding energies range between 2.0 and 3.2 kcal mol^1 for the A complexes and between 1.5 and 1.7 kcal mol~'for the B complexes.The frequency shifts are calculated for the CH1D2D3X isotopomers.Both A and B complexes exhibit simultaneously an elongation of the OH bond and a red shift and an infrared intensity increase of the corresponding OH stretching vibration along with a contraction of the CHI bond,a blue shift,and an infrared intensity decrease of the CHI stretching vibration.The interaction of CH_3F and CH_3C1 with HP also induces a contraction of the external CH_2 and CH_3 bonds and a blue shift of the corresponding stretching vibrations.The results of an NBO analysis are discussed in terms of the hyperconjugation and rehybridization model.While there is a charge transfer from CH_3X to HP in the A complexes,the charge transfer is negligible in the B complexes.Complex formation results in an increase of the occupation of the sigma(OH)and sigma(CHl)antibonding orbitals and an increase of the s-character of the corresponding O or C atoms.In contrast,there is a decrease in the occupation of the sigma(CH2)and sigma(CH3)orbitals.The n(X)->sigma(OH)hyperconjugative energies are equal to approx10 kcal mol~(-1),and the n(O)->sigma(CH)hyperconjugative energies range between 1.4 and 2.5 kcal mol~(-1)for the A complexes.Our results show that the OH bond lengths are mainly determined by the occupation of the sigma(OH)orbitals.The CH distances depend on both the occupation of the sigma(CH)orbitals and the hybridization of the corresponding C atom.
机译：使用MP2 / 6-31 + G（d，p）计算来分析CH_3X（X = F，Cl或Br）与过氧化氢（HP）之间的相互作用。在每个上发现两个稳定的结构A和B势能表面。A配合物的特征是六元结构，B配合物的稳定性较低，五元结构。在两种配合物中，分子都被OH…X和CHI…O结合在一起。氢键：A配合物的结合能在2.0至3.2 kcal mol ^ 1之间，B配合物的结合能在1.5至1.7 kcal mol-1之间。计算CH1D2D3X异构体的频移，A和B配合物同时显示CH_3F和OH的相互作用是OH键伸长和相应的OH拉伸振动的红移和红外强度增加以及CHI键的收缩，蓝移和CHI拉伸振动的红外强度降低。具有HP的CH_3C1也诱导外部CH_2和C的收缩H_3键和相应拉伸振动的蓝移。根据超共轭和再杂交模型讨论了NBO分析的结果。尽管A配合物中CH_3X到HP发生了电荷转移，但在A络合物中电荷转移可忽略不计络合物的形成导致sigma（OH）和sigma（CHl）反键轨道的占据增加，并且相应的O或C原子的s-字符增加。 n（X）-> sigma（OH）超共轭能约等于10 kcal mol〜（-1），n（O）-> sigma（ A配合物的CH）超共轭能在1.4和2.5 kcal mol〜（-1）之间。我们的结果表明，OH键的长度主要取决于sigma（OH）轨道的占据.CH距离取决于两个σ（CH）轨道的占据和相应C原子的杂化。

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