传能反应O(~1D)+CO_2(~1∑_g^+)→O(~3P)+CO_2(~1∑_g^+)中间物机理的理论研究

Theoretical Studies on the Intermediate Complex Mechanism ofthe Energy Transfer Reaction of O(~1D)+CO_2(~1∑_g^+)→O(~3P)+CO_2(~1∑_g^+)

利用 ab initio量子化学方法研究了自旋禁阻的传能反应 O( 1D) +CO2 ( 1Σ+ g ) O( 3 P) +CO2 ( 1Σ+ g )的反应机制 ,通过中间化合物 CO3 的单、三重态的势能面交叉点的确认 ,证明了中间物传能机理的可行性 .同时计算了交叉点处的自旋 -轨道偶合和面间跃迁几率 ,进一步证明了中间化合物 CO3 的形成在传能过程中的重要作用 .

The reaction mechanism of spin-forbidden energy transfer reaction O( 1D)+CO 2( 1Σ + g) O( 3P)+CO 2( 1Σ + g) was investigated by ab initio quantum chemistry methods. The conical intersection of the two surfaces of CO 3 intermediate complex with multipl-spin electronic states was searched by using CASSCF(6,8) /6-311G * method. The intermediate complex channel are supported by the calculations of spin-orbit coupling and transition probability.