Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
J Chem Phys. 2013 Jan 14;138(2):024308. doi: 10.1063/1.4774026.
The adiabatic state-to-state dynamics of the reaction between O((3)P) and NH(X(3)Σ(-)) has been investigated on three lowest-lying electronic states, namely, the X(1)A('), A(1)A("), and a(3)A(") states, using the recently developed global potential energy surfaces based on high level ab initio data. The reaction rate has contributions from all three states, with the largest coming from the triplet state. The rotational and vibrational degrees of freedom of the prominent NO product are highly excited, although significant differences exist in the internal state distributions of the three adiabatic channels. The reaction proceeds with a complex-forming mechanism on all three electronic states, as evidenced by resonance structures in reaction probabilities and the near forward-backward symmetry in the differential cross section. However, significant non-reactive scattering and inverted vibrational state distributions suggest substantial non-statistical behaviors.
O((3)P)和 NH(X(3)Σ(-))之间的绝热态-态动力学反应已在三个最低电子态 X(1)A(')、A(1)A(")和 a(3)A(")上进行了研究，所使用的是基于高精度从头算数据的最近开发的全局势能面。该反应的速率来自于所有三个态，其中最大的贡献来自三重态。显著的 NO 产物的转动和振动自由度高度激发，尽管三个绝热通道的内部态分布存在显著差异。反应在所有三个电子态上都遵循复杂形成机制，这可以从反应概率中的共振结构和微分截面中的近乎前后对称看出。然而，显著的非反应散射和反转的振动态分布表明存在大量非统计行为。
