The reaction mechanism of OXO(X=Cl, Br) with H(2\%S\%) was studied theoretically by using the B3LYP/6-311+G(3df, 3pd) and the high-level electron-correlation QCISD(T)/6-311+G ** at single-point. The results show that ...The reaction mechanism of OXO(X=Cl, Br) with H(2\%S\%) was studied theoretically by using the B3LYP/6-311+G(3df, 3pd) and the high-level electron-correlation QCISD(T)/6-311+G ** at single-point. The results show that the mechanism for the title reaction involves three channels, from which OH+XO, HO 2+X and HX+O 2 products could be obtained, respectively. Therefore, the channel to yield the products OH+XO is the dominant one in agreement with the experiments.展开更多
A new Zn(Ⅱ)coordination polymer,[Zn(nba)2(mbix)]2n(1,Hnba=4-nitrobenzoic acid,mbix=1,3-bis(imidazol-1-ylmethyl)-benzene),was synthesized and characterized by elemental analyses,IR spectra,TG,fluorescence spectroscopy...A new Zn(Ⅱ)coordination polymer,[Zn(nba)2(mbix)]2n(1,Hnba=4-nitrobenzoic acid,mbix=1,3-bis(imidazol-1-ylmethyl)-benzene),was synthesized and characterized by elemental analyses,IR spectra,TG,fluorescence spectroscopy,single-crystal and powder X-ray diffractions.It belongs to the triclinic system,P1 space group,with a=9.341(2),b=13.029(3),c=23.660(6)A,α=99.603(6)°,β=90.461(6)°,γ=90.597(5)°,V=2838.9(12)?3 and Z=2.It shows one-dimensional chains which are further linked by C–H···O hydrogen bonds andπ-πstacking interactions to yield a three-dimensional supramolecular structure.In addition,the Natural Bond Orbital(NBO)was analyzed in using the PBE0/LANL2DZ method built in Gaussian 09 Program.The calculation results indicated obvious covalent interaction between the coordinated atoms and Zn(Ⅱ)ion.展开更多
Two new coordination polymers, [Zn(bba)_2(bib)]_(2n)(1) and [Co_(0.5)(bba)(bib)_(0.5)]_(2n)(2)(Hbba = 4-bromobenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane), have been hydrothermally designed and synthesized, and t...Two new coordination polymers, [Zn(bba)_2(bib)]_(2n)(1) and [Co_(0.5)(bba)(bib)_(0.5)]_(2n)(2)(Hbba = 4-bromobenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane), have been hydrothermally designed and synthesized, and their structures were determined by elemental analyses, IR spectroscopy, TG, fluorescence spectroscopy, X-ray single-crystal and powder diffraction. Complexes 1 and 2 both belong to the monoclinic system and exhibit one-dimensional zigzag chain-like structure. In addition, we analyzed Natural Bond Orbital(NBO) in using the PBE0/LANL2 DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Zn(Ⅱ), Co(Ⅱ) ions.展开更多
The reaction mechanism of OBrO with OH has been studied using the B3LYP/6-311+G(d,p) and the high-level electron-correlation CCSD(T)/6-311+G(d,p) at single-point. The results show that the title reaction could probabl...The reaction mechanism of OBrO with OH has been studied using the B3LYP/6-311+G(d,p) and the high-level electron-correlation CCSD(T)/6-311+G(d,p) at single-point. The results show that the title reaction could probably proceed by four possible schemes, generating HOBr+O2, HBr+O3, BrO+HO2 and HOBrO2 products, respec-tively. The main channel is the one to yield HOBr+O2. The whole reaction involves the formation of three-membered, four-membered and five-membered rings, followed by the complicated processes of association, H-shift, Br-shift and dissociation. All routes are exothermic.展开更多
The mechanism and dynamical properties for the reaction of NCS and OH radicals have been investigated theoretically. The minimum energy paths (MEP) of the reaction were calculated using the density functional theory (...The mechanism and dynamical properties for the reaction of NCS and OH radicals have been investigated theoretically. The minimum energy paths (MEP) of the reaction were calculated using the density functional theory (DFT) at the B3LYP/6-311+G** level, and the energies along the MEP were further refined at the QCISD(T)/6-311+G** level. As a result, the reaction mechanism of the title reaction involves three channels, producing HCS+NO and HNC+SO products, respectively. Path I and path II are competitive, with some advantages for path I in kinet-ics. As for path III, it looks difficult to react for its high energy barrier. Moreover, the rate constant have been cal-culated over the temperature range of 8002500 K using canonical variational transition-state theory (CVT). It was found that the rate constants for both path I and path II are negatively dependent on temperature, which is similar with the experimental results for reactions of NCS with NO and NO2, and the variational effect for the rate constant calculation plays an important role in whole temperature range.展开更多
文摘The reaction mechanism of OXO(X=Cl, Br) with H(2\%S\%) was studied theoretically by using the B3LYP/6-311+G(3df, 3pd) and the high-level electron-correlation QCISD(T)/6-311+G ** at single-point. The results show that the mechanism for the title reaction involves three channels, from which OH+XO, HO 2+X and HX+O 2 products could be obtained, respectively. Therefore, the channel to yield the products OH+XO is the dominant one in agreement with the experiments.
基金This project was supported by the Science and Technology Project of Jilin Provincial Education Department(JJKH20220828KJ)the Natural Science FoundationofChangchunNormal University(2020-005).
基金supported by the Science and Technology development plan of Jilin Province(2015052006JH)
文摘A new Zn(Ⅱ)coordination polymer,[Zn(nba)2(mbix)]2n(1,Hnba=4-nitrobenzoic acid,mbix=1,3-bis(imidazol-1-ylmethyl)-benzene),was synthesized and characterized by elemental analyses,IR spectra,TG,fluorescence spectroscopy,single-crystal and powder X-ray diffractions.It belongs to the triclinic system,P1 space group,with a=9.341(2),b=13.029(3),c=23.660(6)A,α=99.603(6)°,β=90.461(6)°,γ=90.597(5)°,V=2838.9(12)?3 and Z=2.It shows one-dimensional chains which are further linked by C–H···O hydrogen bonds andπ-πstacking interactions to yield a three-dimensional supramolecular structure.In addition,the Natural Bond Orbital(NBO)was analyzed in using the PBE0/LANL2DZ method built in Gaussian 09 Program.The calculation results indicated obvious covalent interaction between the coordinated atoms and Zn(Ⅱ)ion.
基金The project was supported by the Science and Technology development plan of Jilin province(2015052006JH)
文摘Two new coordination polymers, [Zn(bba)_2(bib)]_(2n)(1) and [Co_(0.5)(bba)(bib)_(0.5)]_(2n)(2)(Hbba = 4-bromobenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane), have been hydrothermally designed and synthesized, and their structures were determined by elemental analyses, IR spectroscopy, TG, fluorescence spectroscopy, X-ray single-crystal and powder diffraction. Complexes 1 and 2 both belong to the monoclinic system and exhibit one-dimensional zigzag chain-like structure. In addition, we analyzed Natural Bond Orbital(NBO) in using the PBE0/LANL2 DZ method built in Gaussian 03 Program. The calculation results indicated the obvious covalent interaction between the coordinated atoms and Zn(Ⅱ), Co(Ⅱ) ions.
基金Project supported by Ministry of Education (the training project of elitist) Foundation ([2001] 3) and the Young Teacher Fund of Northeast Normal University (No. 111382).
文摘The reaction mechanism of OBrO with OH has been studied using the B3LYP/6-311+G(d,p) and the high-level electron-correlation CCSD(T)/6-311+G(d,p) at single-point. The results show that the title reaction could probably proceed by four possible schemes, generating HOBr+O2, HBr+O3, BrO+HO2 and HOBrO2 products, respec-tively. The main channel is the one to yield HOBr+O2. The whole reaction involves the formation of three-membered, four-membered and five-membered rings, followed by the complicated processes of association, H-shift, Br-shift and dissociation. All routes are exothermic.
基金Project supported by the Natural Science Foundation of Jilin Province (No. 20010344) the Foundation of Education Bureau of Hainan Province (No. hjkj200312) and the Science Foundation for Excellent Youth of Northeast Normal University (No. 111382).
文摘The mechanism and dynamical properties for the reaction of NCS and OH radicals have been investigated theoretically. The minimum energy paths (MEP) of the reaction were calculated using the density functional theory (DFT) at the B3LYP/6-311+G** level, and the energies along the MEP were further refined at the QCISD(T)/6-311+G** level. As a result, the reaction mechanism of the title reaction involves three channels, producing HCS+NO and HNC+SO products, respectively. Path I and path II are competitive, with some advantages for path I in kinet-ics. As for path III, it looks difficult to react for its high energy barrier. Moreover, the rate constant have been cal-culated over the temperature range of 8002500 K using canonical variational transition-state theory (CVT). It was found that the rate constants for both path I and path II are negatively dependent on temperature, which is similar with the experimental results for reactions of NCS with NO and NO2, and the variational effect for the rate constant calculation plays an important role in whole temperature range.
