HCO自由基与NO反应的量子化学研究(英文)

Quantum Chemical Study on the Reaction of Formyl Radical with Nitric Oxide

对HCO(2A’)自由基与NO(2πu)在单线态势能面上的反应进行了量子化学研究.分别在B3LYP/6-311++G(3df,3pd)和MP2/6-311++G(3df,3pd)水平优化了反应势能面上各驻点的几何结构,获得相应的振动频率和零点振动能.在QCISD(T)/6?311++G(3df,3pd)水平精确计算了各驻点的能量.通过内禀反应坐标计算确认了所有过渡态,用过渡态理论计算了反应速率常数.确定了反应机理,理论预测的优势产物是与实验相吻合的HNO(1A’)和CO(1Σg+).

The gas-phase reaction of the HCO （^2 A＇ ） radical with NO （^2πu ） onthe singlet potential energy surfaces wasinvestigated bymeans of the MP＇2 and B3LYP theories with the 6-311 ＋ ＋ G （3df,3pd） basis set. The geometries for all the stationary points were fully optimized. The accurate single-point energies of all species were computedat the QCISD（T）/6 311 ＋ ＋ G（ 3df, 3pd） level. In addition, the intrinsic reactioneoordinate analysis was performed at the B3LYP/6-311 ＋ ＋ G（3df, 3pd） level, and rate coefficients were computed by using transition state theory. The reactionmechanismwas analyzed in detail. The predicted dominant products are HNO（^1A＇ ） and CO （^1∑g^＋）.