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DFT and ab initio Studies on Stability and Isomerization of Benzofuroxan
Li Jinshan1,2, Xiao Heming1, Dong Haishan2
1.Department of Chemistry,Nanjing University of Science and Technology,Nanjing 210094;2.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1,2, 肖鹤鸣1, 董海山2
1.南京理工大学化学系南京 210094;2.中国工程物理研究院化工材料研究所绵阳 621900
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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