Acta Phys. -Chim. Sin. ›› 2003, Vol. 19 ›› Issue (06): 481-486.doi: 10.3866/PKU.WHXB20030601

• ARTICLE •     Next Articles

Experimental and Theoretical Study on the Reaction of CCl2+H2O

Liu Yun-Zhen;Hu Chang-Jin;Pei Lin-Sen;Chen Cong-Xiang;Ma Xing-Xiao   

  1. Open Laboratory of Bond Selective Chemistry, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026
  • Received:2002-10-14 Revised:2003-02-26 Published:2003-06-15
  • Contact: Chen Cong-Xiang

Abstract: Absolute rate constant for the reaction of CCl2 radical with H2O is obtained as (5.45±0.95)×10-14 cm3•molecule-1•s-1 by LPLIF technique. The CCl2 is first produced by 213 nm laser photolysis of CCl4. The mechanism for the reaction CCl2+H2O has been studied using a highlevel ab initio G2MP2 method. It is found that there are two reaction mechanisms: insertion and additionelimination. The three primary product channels, HCl+HClCO, HCl+transClCOH and HCl+cisClCOH, are studied in detail. Moreover, the branch ratios are calculated using RRKMTST and convention transition state theories. The calculations show that at lower temperatures the major product channel is HCl+HCClO via the insretion of C atom of CCl2 into OH bond of H2O, whereas the formation of HCl+transClCOH dominates at higher temperatures.

Key words: CCl2 radical, Rate constant, Ab initio theoretical calculation,