过渡态理论对Arrhenius公式的诠释——以硝酸异丙酯与自由基反应为例

孙翠红, 许保恩, 刘迎, 杨静, 吕立强

Interpretation of Arrhenius Formula by Transition State Theory: Taking the Reaction of Isopropyl Nitrate with Radicals as an Example

Cuihong Sun, Baoen Xu, Ying Liu, Jing Yang, Liqiang Lv

表1 IPN + Cl、IPN + OH、IPN + NO3三个反应体系中反应物、过渡态的电子能、零点能及相对能量

反应体系 IPN + Cl IPN + OH IPN + NO3 R TS R TS R TS εele/(a.u.) −857.5943 −677.6695 −857.5996 −677.6777 −857.5801 −677.6596 εele, rel/(kJ∙mol−1) 0.00 15.77 0.00 7.98 0.00 25.88 ZPE/(a.u.) 0.1120 0.1251 0.1123 0.1265 0.1042 0.1229 εele + ZPE/(a.u.) −857.4823 −677.5444 −857.4872 −677.5512 −857.4759 −677.5368 (εele + ZPE)rel/(kJ∙mol−1) 0.00 −5.03 0.00 2.27 0.00 20.10