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DFT and ab initio Studies on Stability and Isomerization of Benzofuroxan
Li Jinshan,Xiao Heming,Dong Haishan
Author NameAffiliation
Li Jinshan Department of Chemistry,Nanjing University of Science and Technology,Nanjing 210094; Institute of Chemical Materials,China Academy of Engineering Physics,Mianyang 621900 
Xiao Heming Department of Chemistry,Nanjing University of Science and Technology,Nanjing 210094 
Dong Haishan Institute of Chemical Materials,China Academy of Engineering Physics,Mianyang 621900 
Abstract:
B3LYP/6-31G(d)-DFT(Density Functional Theory)method has been employed to study benzofuroxan,o-dinitrosobenzene and the isomerization between them.The calculated results with B3LYP/6-31G(d)-DFT show:(1)the molecular total energy of benzofuroxan is lower than that of o-dinitrosobenzene;(2)the activation energy(Ea+=51.0kJ/mol)of forward reaction that benzofuroxan isomerises into o-dinitrosobenzene,is in agreement with the experimental(58.6kJ/mol)provided by reference,and the activation energy(Ea-=4.6kJ/mol)of back-ward reaction is very small.It is concluded thereby that benzofuroxan is more stable than o-dinitrosobenzene.In addition,the corresponding ab initio calculations at the level of HF/3-21G,HF/6-31G(d)and MP2/6-31G(d)//6-31G(d) were completed,and it was found that the calculated results by B3LYP-DFT method are superior to those from ab initio calculation.The calculations of harmonic vibrational frequencies with B3LYP/6-31G(d)theoretically supported that o-dinitrosobenzene is the intermediate of “self-self”tautomeric rearrangement of benzofuroxan.
Key words:  Benzofuroxan,Isomerization,B3LYP-DFT method,ab initio method,Vibrational frequency
FundProject:中国工程物理研究院科学基金资助项目(99050330)
苯并氧化呋咱稳定性和异构化的DFT和ab initio研究
李金山,肖鹤鸣,董海山
摘要:
运用B3LYP/6-31G(d)密度泛函理论(DFT)方法对苯并氧化呋咱、邻二亚硝基苯及其间的异构化反应进行了计算研究。结果表明,苯并氧化呋咱的分子总能量比邻二亚硝基苯的低;由苯并氧化呋咱异构为邻二亚硝基苯的正向反应活化能(Ea+=51.0kJ/mol),与文献实测值(58.6kJ/mol)较接近,而其逆向反应活化能(Ea-=4.6kJ/mol)很小,从而揭示了苯并氧化呋咱比邻二亚硝基苯更稳定·此外,进行了HF/3-21G、HF/6-31G(d)和MP2/6-31G(d)//6-31G(d)水平下相应的计算,发现B3LYP-DFT的结果较abinitio为优。谐振动频率的B3LYP/6-31G(d)计算还支持了邻二亚硝基苯为苯并氧化呋咱“自-自”互变重排反应的中间体。
关键词:  苯并氧化呋咱  异构化  B3LYP-DFT方法  ab initio方法  振动频率
DOI:10.1088/1674-0068/13/1/55-60
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