Instituto de Física Fundamental (CSIC), Serrano 123, 28006 Madrid, Spain.
J Chem Phys. 2012 Apr 28;136(16):164309. doi: 10.1063/1.4705426.
The dynamics of the C((3)P)+OH(X(2)Π) → CO(a(3)Π)+H((2)S) on its second excited potential energy surface, 1(4)A", have been investigated in detail by means of an accurate quantum mechanical (QM) time-dependent wave packet (TDWP) approach. Reaction probabilities for values of the total angular momentum J up to 50 are calculated and integral cross sections for a collision energy range which extends up to 0.1 eV are shown. The comparison with quasi-classical trajectory (QCT) and statistical methods reveals the important role played by the double well structure existing in the potential energy surface. The TDWP differential cross sections exhibit a forward-backward symmetry which could be interpreted as indicative of a complex-forming mechanism governing the dynamics of the process. The QM statistical method employed in this study, however, is not capable to reproduce the main features of the possible insertion nature in the reactive collision. The ability to stop individual trajectories selectively at specific locations inside the potential energy surface makes the QCT version of the statistical approach a better option to understand the overall dynamics of the process.
C((3)P)+OH(X(2)Π) → CO(a(3)Π)+H((2)S) 在其第二激发势能面上的动力学，1(4)A"，已通过精确的量子力学（QM）时变波包（TDWP）方法进行了详细研究。计算了总角动量 J 值高达 50 的反应概率，并显示了扩展到 0.1 eV 的碰撞能量范围内的积分截面。与准经典轨迹（QCT）和统计方法的比较揭示了势能面中存在双势阱结构所起的重要作用。TDWP 微分截面表现出前后对称，这可以解释为控制过程动力学的复杂形成机制的指示。然而，本研究中采用的 QM 统计方法无法再现反应碰撞中插入性质的主要特征。能够选择性地将单个轨迹停留在势能面内的特定位置，使得统计方法的 QCT 版本成为更好的选择，可以理解过程的整体动力学。
