Yan Wei, Tan Rui Shan, Lin Shi Ying
School of Physics , Shandong University , Jinan 250100 , China.
School of Science , Shandong Jianzhu University , Jinan 250101 , China.
J Phys Chem A. 2019 Apr 4;123(13):2601-2609. doi: 10.1021/acs.jpca.9b00508. Epub 2019 Mar 21.
The dynamics of the reactive scatterings of the ground (Na(3S)) and first excited (Na(3P)) state sodium atoms from hydrogen fluoride (HF) molecules is investigated by performing comprehensive Coriolis-coupled quantum wave packet calculations on the recent ab initio potential energy surface (PES). In the Na(3S) + HF reaction, the nonadiabatic effect is found to be negligibly small, and the reactivity is significantly promoted by the initial vibrational excitations being in line with the available experimental result. Excellent quantitative agreement between theory and experiment is also achieved for the initial state specified integral cross sections and rate constants for v ≥ 3 vibrational states. However, the calculated rate constant for v = 2 significantly underestimates the experimental result. The possible cause for the disagreement is discussed in detail. For the Na(3P) + HF scattering, which can lead to the formation of either the ground state NaF + H product or Na(3S) + HF reactant via the harpooning process, the calculated result for the integral cross section shows excellent agreement with the available experimental result indicating the reasonable accuracy of the interstate coupling term of the employed PES.
通过在最新的从头算势能面（PES）上进行全面的科里奥利耦合量子波包计算，研究了基态（Na(3S)）和第一激发态（Na(3P)）钠原子与氟化氢（HF）分子反应散射的动力学。在Na(3S) + HF反应中，发现非绝热效应小到可以忽略不计，并且初始振动激发显著促进了反应活性，这与现有的实验结果一致。对于v≥3振动态的初始态指定积分截面和速率常数，理论与实验也取得了极好的定量吻合。然而，v = 2时计算得到的速率常数显著低估了实验结果。详细讨论了不一致的可能原因。对于Na(3P) + HF散射，其可通过“刺取”过程导致基态产物NaF + H或反应物Na(3S) + HF的形成，积分截面的计算结果与现有的实验结果显示出极好的吻合，表明所采用的PES的态间耦合项具有合理的准确性。
