物理化学学报 >> 2006, Vol. 22 >> Issue (09): 1047-1051.doi: 10.1016/S1872-1508(06)60045-4

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DMP与DEP在凝聚相中裂解反应理论研究: 隧道效应与溶剂效应

姜辉;吴韬;李浩然   

  1. 浙江大学化学系, 杭州 310027
  • 收稿日期:2006-01-23 修回日期:2006-03-14 发布日期:2006-09-04
  • 通讯作者: 李浩然 E-mail:lihr@zju.edu.cn

Theoretical Study on the Decomposition of DMP and DEP in Condensed Phase∶Solvent Effect and Tunneling Effect

JIANG Hui;WU Tao;LI Hao-Ran   

  1. Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China
  • Received:2006-01-23 Revised:2006-03-14 Published:2006-09-04
  • Contact: LI Hao-Ran E-mail:lihr@zju.edu.cn

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摘要： 采用密度泛函理论(DFT)B3LYP方法, 以极化连续模型(PCM)和导体反应场模型(COSMORS)的溶剂模型为基础, 结合反应动力学研究了2,2-二甲氧基丙烷(DMP)与2,2-二乙氧基丙烷(DEP)在凝聚相(溶液相)中的裂解反应. 结果表明, 四元环过渡态裂解反应机理是DMP与DEP裂解反应的主反应通道, 溶剂效应和隧道效应对液相中的裂解反应速率有较大的影响, 而且溶剂效应的影响更显著. 在凝聚相反应理论研究中, 溶剂效应和量子隧道效应都是不能忽略的因素.

关键词: 凝聚相, 溶剂效应, 隧道效应, 速率常数, 裂解反应

Abstract: A systemic theoretical study on the decomposition of 2,2-dimethoxypropane (DMP) and 2,2-diethoxy- propane (DEP) in condensed phase has been carried out. The four-center cyclic transition state is studied using the B3LYP method in DFT, using the PCM and COSMORS models within the self-consistent reaction filed (SCRF) theory. The results indicate that the solvent effect and tunneling effect must be taken into account in determining the rate constant of the decomposition reaction in the condensed phase.

Key words: Condensed phase, Solvent effect, Tunneling effect, Rate constant, Decomposition reaction