高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (9): 1727.

• 研究论文 • 上一篇    下一篇

乙硼烷离子和自由基异构体重排与体系势能面的量子化学计算研究

孙延波, 吴迪, 李泽生, 黄旭日, 孙家锺   

  1. 吉林大学理论化学研究所理论化学计算国家重点实验室, 长春 130023
  • 收稿日期:2002-04-17 出版日期:2002-09-24 发布日期:2002-09-24
  • 通讯作者: 孙延波(1973年出生),男,博士,讲师,从事理论化学研究.E-mail:ranier@sina.com.cn E-mail:ranier@sina.com.cn
  • 基金资助:

    国家自然科学基金(批准号:2007301429892168);教育部科技重点项目博士点基金;骨干教师计划资助

The Quantum Chemistry Calculation Studies on Rearrangement, Ionization and Potential Energy Surface of B2H5 Radical and Cation

SUN Yan-Bo, WU Di, LI Ze-Sheng, HUANG Xu-Ri, SUN Chia-Chung   

  1. Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, China
  • Received:2002-04-17 Online:2002-09-24 Published:2002-09-24

PDF (PC)

被引次数

10

摘要： 在B3LYP/6-311G(d,p)和QCISD(T)/6-311+ +G(3df,2p)(单点)水平下,对B2H5+阳离子和B2H5·自由基全优化得到9个几何异构体:B2H5+单态体系(D3h,C1),B2H5+三重态(Cs,Cs,C1),B2H5·自由基(C2v,Cs,Cs,Cs).得到势能面上与体系异构化过程相联系的5种过渡态.

关键词: 势能面, 异构化, 绝热电离能, 过渡态

Abstract: Ab initio calculations for B2H5+ cation and neutral B2H5· radical have been performed at B3LYP/6-311G(d,p) and QCISD(T)/6-311+ +G(3df,2p)(single-point) level to give nine isomers, i.e. for B2H5+, there are two singlets(D3h, C1) and three triplets(Cs, C1, C1); for B2H5·, there are four singlets(C2v, Cs, Cs, Cs). The calculated results also give five transition states associated with the isomers. The adiabatic ionization potentials of the two B2H5· radicals(singly bridged C2v) and (doubly bridged Cs) are 6.84 and 7.65 eV, respectively. For the B2H5+, the energy difference between the most stable triplet state(singly bridged Cs) and the lowest singlet state(triply bridged D3h) is 4.72 eV. For the B2H5· and B2H5+ systems, the calculated results are in accordance with the experiments of R?s?i`?.

Key words: Potential energy surface, Isomerization, Adiabatic ionization potential, Transition state

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