NCO自由基与O和N反应的理论研究

Theoretical Study of the Reaction of NCO Radical with O,N atoms

采用密度泛函和量子化学从头算方法,对NCO自由基和O,N原子反应的势能面进行了理论研究,讨论了主要的反应通道.这两种自由基反应的机理比较类似,初始都有两种进攻方式.NCO与O的主反应通道是O原子从N端无势垒加合,经过一低垒过渡态,得到稳定产物P1(CO+NO),而对NCO与N反应得到了一完整反应通道和无垒加合产物.

The potential energy surface of radical-radical reactions between NCO and O, N were investigated theoretically with the density function theory and ab inito method at C CSD （T）/6-311 G（d）//B3 LYP/6-311 G （d） level. The main reaction paths were discussed. The mechanisms of the two reactions are similar, and both have two initial association ways. For the reaction NCO ＋ O, the reaction path through which O atom was initially associated with N atom of NCO and then the adduct passed a low barrier to yield product P1 （ CO ＋ NO） is the most favorable path. For the reaction NCO ＋ N, one reaction path was found and the initial intermediate complex was obtained by a barrierless process for N-N association.