南极冰表面上ClONO_2与Cl^-的反应机理研究  

Study of reaction mechanism of ClONO_2 with Cl^- on ice surface of the South Pole

作　　者：方芳[1] 迟绍明[1] 田国才[1] 陶建民[1] 李国宝[1] 

机构地区：[1]云南师范大学化学化工学院,云南昆明650092

出　　处：《云南大学学报（自然科学版）》2005年第1期64-70,共7页Journal of Yunnan University(Natural Sciences Edition)

基　　金：国家自然科学基金资助项目(29763002);云南省自然科学基金资助项目(2002B0032M).

摘　　要：采用密度泛函理论计算方法B3LYP和基组6-31G(d,p),对ClONO2+Cl-(H2O)n→Cl2+NO-3(H2O)n(n=0,1,2)的反应机理进行了理论计算研究.研究发现,随着参与反应的水分子数n的增加,反应活化能垒降低.计算结果表明,在冰表面上,水一方面通过氢键的参与形成环形团簇复合物降低活化能;另一方面,水分子作为桥,辅助分子间质子发生迁移,加快反应进程,对反应起到一定的催化作用.这与实验观察到的结果相一致.The reaction mechanism of ClONO_2+Cl^-(H_2O)_n→Cl_2+NO^-_3(H_2O)_n(n=0,1,2) has been studied by using B3LYP/6-31G(d,p) method.The results show that the activation energy barrier drops drastically as the increase of number of water molecules involved in the reaction.Water molecules should participate the formation of circular compound through hydrogen band and reduce energy barrier.At same time,water molecules should act as a bridge,which makes protons transfer easily on ice.The deduction is agreed with experimental results.

关 键 词：B3LYP 基组 能垒 反应机理 密度泛函理论 Cl^- 水分子 间质 实验观察 辅助 

分 类 号：N8[自然科学总论] O641[理学—物理化学]