从头算和RRKM理论研究O（^1D）＋trans-CH2FCH2F反应  

Ab Initio and RRKM Study on O（^1D）＋trans-CH2FCH2F Reaction

作　　者：宋崇富[1,2] 田志美[1] 柴兰兰[1] 

机构地区：[1]阜阳师范学院化学化工学院,安徽阜阳236041 [2]浙江大学生命科学学院,浙江杭州310058

出　　处：《贵州大学学报（自然科学版）》2012年第3期9-12,18,共5页Journal of Guizhou University:Natural Sciences

基　　金：国家自然科学基金(20971024);安徽省高等学校省级自然科学研究项目(KJ2010B161;KJ2010B150);分析化学重点学科(2010xk7-02)

摘　　要：运用MP2/6-311G(d,p)方法优化得到了O(1D)+trans-CH2FCH2F反应势能面上稳定点的优化几何构型和振动频率。精算的能量是在QCISD(T)/6-311++G(d,p)水平上得到的。RRKM(Rice-Ramsperger-Kassel-Marcus)理论用来计算碰撞能在0-350 kcal/mol范围内通过中间体的微正则速率常数。计算得出,当碰撞能低于140 kcal/mol时标题反应的主要产物是HF和CH2F;碰撞能在140-350 kcal/mol时反应的主要产物是HF,CH2F和OH.在整个碰撞能范围内,HF和CH2F是主要产物。Optimized geometries,vibrational frequencies of the stationary points on the potential energy surface of O（1D） ＋ trans-CH2FCH2F reaction were obtained by MP2/6-311G（d,p） method.The refined energies were calculated at the QCISD（T）/6-311＋＋G（d,p） level of theory.RRKM（Rice-Ramsperger-Kassel-Marcus） theory was used to calculate the microcanonical rate constants at the collisional energies of 0-350 kcal/mol.According to the calculated results,the main products of the title reaction are HF and CH2F when the collisional energy is smaller than 140 kcal/mol.HF,CH2F and OH are the main products of the title reaction when the collisional energy is in the range of 140-350 kcal/mol.HF and CH2F are the main products in the whole range of the collisional energy.

关 键 词：O(1D)+trans-CH2FCH2F MP2/6-311G(d p) 微正则速率常数 RRKM理论 

分 类 号：O643[理学—物理化学]