Li Yida, Wang Yuping, Wang Dunyou
College of Physics and Electronics, Shandong Normal University , Jinan 250014, Shandong China.
J Phys Chem A. 2017 Apr 13;121(14):2773-2779. doi: 10.1021/acs.jpca.7b01547. Epub 2017 Apr 3.
The Polanyi rules on the energy efficiency on reactivity are summarized solely from the locations of barriers on the potential energy surfaces. Here, our quantum dynamics study for the F + CHCl → FCH + Cl reaction shows that the two potential energy minima in the entrance channel on the potential energy surface play an essential role in energy efficiency on reactivity. The reactivity of this reaction is dominated by the low collision energies where two distinctive reaction mechanisms involve the two minima in the entrance channel. Overall, the Cl-CH stretching motion and C-H umbrella motion both are more efficient than the translational motion in promoting this reaction. Although this reaction has a negative energy barrier, our study shows that it is the minima in the entrance channel, together with the energy barrier relative to these minima, that determine the energy efficacy on reactivity.
波拉尼关于反应性的能量效率规则完全是根据势能面上势垒的位置总结出来的。在此，我们对F + CHCl → FCH + Cl反应进行的量子动力学研究表明，势能面上入口通道中的两个势能极小值在反应性的能量效率中起着至关重要的作用。该反应的反应性主要由低碰撞能量主导，在低碰撞能量下，两种独特的反应机制涉及入口通道中的两个极小值。总体而言，Cl-CH伸缩运动和C-H伞形运动在促进该反应方面都比平动更有效。尽管该反应具有负能垒，但我们的研究表明，是入口通道中的极小值以及相对于这些极小值的能垒决定了反应性的能量效率。
