Based on the two-component relativistic effective core potential and matched basis sets cc-pwcvnz-pp （n=Q, 5）, combining the completed basis-set extrapolation of electronic correlation energy and the fourth-order po...Based on the two-component relativistic effective core potential and matched basis sets cc-pwcvnz-pp （n=Q, 5）, combining the completed basis-set extrapolation of electronic correlation energy and the fourth-order polynomial fitting technique, the bond length and spectroscopic constants of Hg2 are studied by the coupled cluster theory with spin-orbit coupling. Spin-orbit coupling is included in the post Hartree-Fock procedure, i.e., in the coupled- cluster iteration, to obtain more reliable theoretical results. The results show that our theoretical values agree with the experimental values very well and will be helpful to understand the spectral character of Hg2.展开更多
The static O-H bond parameters including O-H bond length, O-H charge difference, O-H Mulliken population and O-H bond stretching force constant (k) for 17 phenols were calculated by ab initio method HF/6-31G**. In com...The static O-H bond parameters including O-H bond length, O-H charge difference, O-H Mulliken population and O-H bond stretching force constant (k) for 17 phenols were calculated by ab initio method HF/6-31G**. In combination with the O-H bond dissociation enthalpies (BDE) of the phenols determined by experiment, it was found that there were poor correlationships between the static O-H bond parameters and O-H BDE. Considering the good correlationship bt tween O-H BDE and logarithm of free radical scavenging rate constant for phenolic antioxidant, it is reasonable to believe that the ineffectiveness of static O-H bond parameters in characterizing antioxidant activity arises from the fact that they cannot measure the O-H BDE.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
基金Supported by the Start-Up Funds of Xi’an Polytechnic University under Grant No BS1211the Scientific Research Program Funded by Shaanxi Provincial Education Department under Grant No 2013JK0679
文摘Based on the two-component relativistic effective core potential and matched basis sets cc-pwcvnz-pp （n=Q, 5）, combining the completed basis-set extrapolation of electronic correlation energy and the fourth-order polynomial fitting technique, the bond length and spectroscopic constants of Hg2 are studied by the coupled cluster theory with spin-orbit coupling. Spin-orbit coupling is included in the post Hartree-Fock procedure, i.e., in the coupled- cluster iteration, to obtain more reliable theoretical results. The results show that our theoretical values agree with the experimental values very well and will be helpful to understand the spectral character of Hg2.
文摘The static O-H bond parameters including O-H bond length, O-H charge difference, O-H Mulliken population and O-H bond stretching force constant (k) for 17 phenols were calculated by ab initio method HF/6-31G**. In combination with the O-H bond dissociation enthalpies (BDE) of the phenols determined by experiment, it was found that there were poor correlationships between the static O-H bond parameters and O-H BDE. Considering the good correlationship bt tween O-H BDE and logarithm of free radical scavenging rate constant for phenolic antioxidant, it is reasonable to believe that the ineffectiveness of static O-H bond parameters in characterizing antioxidant activity arises from the fact that they cannot measure the O-H BDE.
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.
