H2O分子在HONO+OH→NO_(2)+H_(2)O反应中的催化机制研究  

The catalytic mechanism of HO on the atmospheric reaction of HONO + OH →H_(2)O+NO_(2)

作　　者：曾兆鹏 文明杰 张勇奇 李爱珍 苏颖诗 张田雷[1] ZENG Zhao-Peng;WEN Ming-Jie;ZHANG Yong-Qi;LI Ai-Zhen;SU Ying-Shi;ZHANG Tian-Lei(College of Chemical&Environment Science,Shaanxi University of Technology,Hanzhong 723000,China)

机构地区：[1]陕西理工大学化学与环境科学学院,汉中723000

出　　处：《原子与分子物理学报》2021年第1期88-96,共9页Journal of Atomic and Molecular Physics

基　　金：国家自然科学基金(21603132);陕西省科技厅基金项目(2019JM-336);陕西理工大学研究生创新基金(SLGYCX2022)。

摘　　要：本文采用CCSD(T)-F12a/cc-p VDZ-F12//M06-2X/6-311+G(2df,2p)方法并结合过渡态理论对HONO+OH→H_(2)O+NO_(2)抽氢反应以及H_(2)O参与该反应的微观机理和速率常数进行了理论研究.结果表明,由于复合物HONO…H_(2)O的高浓度和稳定性,我们预测HONO…H_(2)O+OH反应的大气相关性将比H_(2)O…HONO+OH和H_(2)O…OH+cis-HONO明显得多.进一步的速率常数计算结果表明,cisHONO…H_(2)O+OH反应的速率常数比H_(2)O…cis-HONO+OH和H_(2)O…OH+cis-HONO反应大了8~4个数量级.然而,cis-HONO…H_(2)O+OH反应的有效速率常数比无催化剂主反应cis-HONO+OH低了7~3个数量级.表明在实际大气环境中,H_(2)O对HONO+OH反应的催化效果并不明显.The mechanism and rate constant for the HONO + OH → H_(2)O + NO_(2) reaction without and with H_(2)O have been investigated at the CCSD(T)-F12 a/cc-pVDZ-F12//M06-2 X/6-311 + G(2 df,2 p) level of theory,coupled with rate constant calculations by using transition state theory. Due to the fact that HONO…H_(2)O complex has larger stabilization energy and higher concentration at 298 K than those of H_(2)O…HONO and H_(2)O…OH complexes,we predict that the catalytic effect of H_(2)O in HONO…H_(2)O + OH reaction will be more obvious than those in the other two reactions. The further results confirm our predictions that the rate constant of HONO…H_(2)O + OH reaction is larger by 8 ~ 4 orders of magnitude. However,the effective rate constant of the HONO…H_(2)O + OH reaction is 7 ~ 3 orders of magnitude smaller than the main naked reaction of HONO +OH. It shows that the catalytic effect of H_(2)O on HONO + OH reaction is not obvious in the actual atmospheric environment.

关 键 词：HONO OH 催化剂 反应机理 速率常数 

分 类 号：O643[理学—物理化学]