论文部分内容阅读
采用密度泛函和耦合簇理论方法研究了HS与HONO的反应机理.在B3LYP/6-311+G(2df,2p)水平上对HS+HONO反应中的所有物种进行了几何构型优化和频率分析,通过内禀反应坐标(IRC)确认了反应物、过渡态、中间体和产物之间的相关性;采用CCSD(T)/6-311+G(2df,2p)方法获得了各物种的单点能.计算结果表明:HS+HONO的主要反应通道为HS+cis-HONO→p2-cis-IM1→p2-cis-TS→p2-IM2→P2(H_2S+NO_2),其反应活化能为71.26kJ·mol~(-1).
The reaction mechanism between HS and HONO was investigated by using density functional theory and coupled cluster theory. The geometric configurations and frequencies of all species in HS + HONO reaction were optimized at B3LYP / 6-311 + G (2df, 2p) The correlations between reactants, transition states, intermediates and products were confirmed by the intrinsic reaction coordinate (IRC). The CCSD (T) / 6-311 + G (2df, 2p) The results show that the main reaction channel of HS + HONO is HS + cis-HONO → p2-cis-IM1 → p2-cis-TS → p2-IM2 → P2 71.26kJ · mol ~ (-1).