Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China.
J Chem Phys. 2011 Oct 28;135(16):164312. doi: 10.1063/1.3656243.
Quantum state-to-state dynamics for the N((4)S) + OH(X( 2)Π) → H((2)S) + NO(X( 2)Π) reaction is reported on an accurate ab initio potential energy surface of the lowest triplet electronic state (a(3)A(")) of HNO∕HON. It was found that the reaction is dominated by long-lived resonances supported by the HNO and HON wells. Significant non-reactive scattering was observed, indicating substantial deviations from the statistical limit. Due to the large exothermicity of the reaction, the NO product has hot internal state distributions: its rotational state distribution is inverted and peaks near the highest accessible rotational level; and its vibrational state distribution extends to υ = 10 and decays monotonically with the vibrational quantum number. In particular, the predicted product vibrational distribution is in reasonably good agreement with experiment. The calculated differential cross section is dominated by scattering in both the forward and backward directions, consistent with the formation of reaction intermediates.
基于 HNO/HON 最低三重态（a(3)A(")）的高精度从头算势能面，报道了 N((4)S) + OH(X( 2)Π) → H((2)S) + NO(X( 2)Π) 反应的量子态态动力学。研究发现，该反应主要由 HNO 和 HON 势阱支持的长寿命共振所主导。观察到显著的非反应散射，表明与统计极限有很大偏差。由于反应的高放热性，NO 产物具有热的内部态分布：其转动态分布反转，并在最高可达的转动能级附近达到峰值；其振动态分布延伸到 υ = 10 并随着振动量子数单调衰减。特别是，预测的产物振动分布与实验相当吻合。计算的微分截面主要由前向和后向散射主导，与反应中间体的形成一致。
