论文部分内容阅读
用密度泛函方法(DFT)和全活化空间自洽场方法(CASSCF)以及耦合簇理论(CCSD)优化了反式和顺式HOOOH的平衡几何构型,用DFT计算了HOOOH顺反异构化反应的势能曲线和谐振动频率.用含时密度泛函理论(TD-DFT)和二阶全活化空间微扰理论(CASPT2)计算了反式和顺式HOOOH垂直激发能.计算结果表明:(1)反式异构体比顺式异构体稳定;(2)两种稳定构型的异构化反应有两种路径;(3)对于垂直跃迁能最低的单态和叁态,反式的垂直跃迁能比顺式的低;(4)在单激发态中,CASPT2方法预测的顺式HOOOH寿命最长的激发态为21A″,其跃迁能是167.43nm,寿命为1.44×10-5s;反式HOOOH寿命最长的激发态为21A,其跃迁能是165.52nm,寿命为2.07×10-5s.
The equilibrium geometries of trans and cis HOOOH were optimized by density functional theory (DFT) and total activation space self-consistent field method (CASSCF) and coupled cluster theory (CCSD). The HOOOH cis-trans isomerization reaction The vertical excitation energies of trans and cis HOOOH were calculated by the time-dependent density functional theory (TD-DFT) and the second order fully activated perturbation theory (CASPT2). The calculated results show that: (1) (2) There are two pathways for the isomerization reaction of the two stable configurations; (3) for the vertical transition lowest energy single state and the triplet state, trans vertical transition (4) In the single-excited state, CASPT2 predicted the longest life expectancy of cis-HOOOH as 21A ", its transition energy was 167.43nm and its life span was 1.44 × 10-5s. The trans HOOOH longest life expectancy of 21A, the transition energy is 165.52nm, life expectancy of 2.07 × 10-5s.