Quantum chemical study of chlorine-dissociation of oxalyl chloride (ClCO)_2→2Cl+2CO  

作　　者：戴年珍 李宗和 

机构地区：[1]Department of Chemistry, Beijing Normal University, Beijing 100875, China

出　　处：《Science China Chemistry》2003年第1期19-24,共6页中国科学（化学英文版）

基　　金：The authors would like to thank professor Fang D. C. for his helpful discussion. This work was supported by the National Natural Science Foundation of China (Grant No. 29713007).

摘　　要：The multi-bond dissociation dynamics of oxalyl chloride ((ClCO)2) is investigated by ab initio calculation. Dissociation of C-Cl bond of oxalyl chloride in the ground state is of barrierless. After the absorption of a photon, (ClCO)2 is excited to the first excited state and one of its C-Cl bonds is broken to yield Cl and ClCOCO* free radicals. In addition, ClCOCO* with high energy is prone to release energy (Q), and to turn into ClCOCO in the ground state. The energy (Q) is ade-quate for ClCOCO to break down into ClCO and CO, and even for ClCO into Cl and CO. The result is consistent with the experimental data that Kong reported.The multi-bond dissociation dynamics of oxalyl chloride ((ClCO)2) is investigated by ab initio calculation. Dissociation of C-Cl bond of oxalyl chloride in the ground state is of barrierless. After the absorption of a photon, (ClCO)2 is excited to the first excited state and one of its C-Cl bonds is broken to yield Cl and ClCOCO* free radicals. In addition, ClCOCO* with high energy is prone to release energy (Q), and to turn into ClCOCO in the ground state. The energy (Q) is adequate for ClCOCO to break down into ClCOand CO, and even for ClCO into Cl and CO. The result is consistent with the experimental data that Kong reported.

关 键 词：oxalyl chloride  UV photodissociation  multi-bond dissociation  ClCOCO free radical  ab initio. 

分 类 号：O641[理学—物理化学]