Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydrox...Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH<span style="white-space:nowrap;">•</span> (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH<span style="white-space:nowrap;">•</span> radicals are determined by the energies <em>E<sub>orb</sub></em> of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module |<em>E<sub>orb</sub></em>|. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.展开更多
The transition state(TS) and Intrinsic Reaction Coordinate (IRC) for the titled reaction were traced by means of MCSCF/6-31G (210 configurations). The reaction activation energy of this reaction is 140.2KJ/mol. The re...The transition state(TS) and Intrinsic Reaction Coordinate (IRC) for the titled reaction were traced by means of MCSCF/6-31G (210 configurations). The reaction activation energy of this reaction is 140.2KJ/mol. The reaction rate constants of five temperetures were calculated by CVT involving the tunneling effects.展开更多
Fluorine-containing halogenated fluorophenol may have effect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans （PFDDs/Fs）. The mechanism for the atomic H initiated r...Fluorine-containing halogenated fluorophenol may have effect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans （PFDDs/Fs）. The mechanism for the atomic H initiated reactions with complete series of nineteen fluorophenol congeners was studies using the density functional theory. At the MPWB1K,/6-31＋G（d,p） level, the geometries and frequencies of reactants, transition states, and products were obtained, and the accurate energetic values were acquired at the MPWB 1K/6-311 ＋G（3df,2p） level. The rate constants were evaluated by the canonical variational transition-state theory with the small curvature tunneling contribution over a wide temperature range of 600-1000 K. The study shows that the intramolecular hydrogen-bond in the ortho-substituted FPs as well as the inductive effect of the electron-withdrawing fluorine and steric repulsion of multiple substitutions may ultimately be responsible for the relative strength of the O-H bonds in FPs. The results can be used for further studies on PFDD/Fs formation mechanism.展开更多
采用CCSD(T)//B3LYP/6-311+G(d,p)方法研究了Criegee中间体CH_3CHOO与OH自由基反应的微观机理.结果表明,上述反应存在抽氢、加成-分解和氧化3类反应通道,其中,syn-CH3CHOO+OH以抽β-H为优势通道,表观活化能为-4.88 k J/mol;anti-CH_3CHO...采用CCSD(T)//B3LYP/6-311+G(d,p)方法研究了Criegee中间体CH_3CHOO与OH自由基反应的微观机理.结果表明,上述反应存在抽氢、加成-分解和氧化3类反应通道,其中,syn-CH3CHOO+OH以抽β-H为优势通道,表观活化能为-4.88 k J/mol;anti-CH_3CHOO+OH则以加成-分解反应为优势通道,表观活化能为-13.25 k J/mol.在加成-分解和氧化反应通道中,anti-构象的能垒均低于syn-构象,而抽氢反应则是syn-(β-H)的能垒低于anti-构象.速率常数计算表明,anti-构象的加成-分解反应通道具有显著的负温度效应;syn-和anti-构象的氧化通道具有显著的正温度效应.3类反应具有显著不同的温度效应,说明通过改变温度可显著调节3类反应的相对速率.展开更多
文摘Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH<span style="white-space:nowrap;">•</span> (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH<span style="white-space:nowrap;">•</span> radicals are determined by the energies <em>E<sub>orb</sub></em> of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module |<em>E<sub>orb</sub></em>|. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.
文摘The transition state(TS) and Intrinsic Reaction Coordinate (IRC) for the titled reaction were traced by means of MCSCF/6-31G (210 configurations). The reaction activation energy of this reaction is 140.2KJ/mol. The reaction rate constants of five temperetures were calculated by CVT involving the tunneling effects.
基金supported by the National Natural Science Foundation of China(No.21177077,21177076)the Independent Innovation Foundation of Shandong University(No.2012JC030)
文摘Fluorine-containing halogenated fluorophenol may have effect as intermediate species involved in the formation of polyfluorinated dibenzo-p-dioxin/dibenzofurans （PFDDs/Fs）. The mechanism for the atomic H initiated reactions with complete series of nineteen fluorophenol congeners was studies using the density functional theory. At the MPWB1K,/6-31＋G（d,p） level, the geometries and frequencies of reactants, transition states, and products were obtained, and the accurate energetic values were acquired at the MPWB 1K/6-311 ＋G（3df,2p） level. The rate constants were evaluated by the canonical variational transition-state theory with the small curvature tunneling contribution over a wide temperature range of 600-1000 K. The study shows that the intramolecular hydrogen-bond in the ortho-substituted FPs as well as the inductive effect of the electron-withdrawing fluorine and steric repulsion of multiple substitutions may ultimately be responsible for the relative strength of the O-H bonds in FPs. The results can be used for further studies on PFDD/Fs formation mechanism.
文摘采用CCSD(T)//B3LYP/6-311+G(d,p)方法研究了Criegee中间体CH_3CHOO与OH自由基反应的微观机理.结果表明,上述反应存在抽氢、加成-分解和氧化3类反应通道,其中,syn-CH3CHOO+OH以抽β-H为优势通道,表观活化能为-4.88 k J/mol;anti-CH_3CHOO+OH则以加成-分解反应为优势通道,表观活化能为-13.25 k J/mol.在加成-分解和氧化反应通道中,anti-构象的能垒均低于syn-构象,而抽氢反应则是syn-(β-H)的能垒低于anti-构象.速率常数计算表明,anti-构象的加成-分解反应通道具有显著的负温度效应;syn-和anti-构象的氧化通道具有显著的正温度效应.3类反应具有显著不同的温度效应,说明通过改变温度可显著调节3类反应的相对速率.
