Mao Ye, Yuan Jiuchuang, Yang Zijiang, Chen Maodu
Key Laboratory of Materials Modification by Laser, Electron, and Ion Beams (Ministry of Education), School of Physics, Dalian University of Technology, Dalian, 116024, PR China.
Sci Rep. 2020 Feb 25;10(1):3410. doi: 10.1038/s41598-020-60033-2.
The time-dependent wave packet quantum dynamics studies for the Mg(3p) + HD → MgH/MgD + D/H diabatic reaction are carried out for the first time on recently developed diabatic YHWCH potential energy surfaces [Phys. Chem. Chem. Phys., 2018, 20, 6638-6647]. The results of reaction probabilities and total integral cross sections show a dramatic preference to the formation of MgD over MgH owing to the insertion reaction mechanism in the title reaction. The MgD/MgH branching ratio witnesses a monotonic decrease from 10.58 to 3.88 at collision energy range of 0.01 to 0.20 eV, and at the collision energy of 0.114 eV, it is close to the experimental value of 5. The rovibrational state-resolved ICSs of the two channels show the products MgD have higher vibrational excitation and hotter rotational state distributions. The opacity function P(J) suggests that the MgH + D channel and MgD + H channel are dominated by high-b and low-b collisions, respectively. Both forward and backward scattering peaks are found in the differential cross section curves, whereas the angle distributions of products are not strictly forward-backward symmetric because of the short lifetime of the complex in the reaction.
首次在最近开发的非绝热YHWCH势能面上[《物理化学化学物理》，2018，20，6638 - 6647]对Mg(3p) + HD → MgH/MgD + D/H非绝热反应进行了含时波包量子动力学研究。反应概率和总积分截面的结果表明，由于标题反应中的插入反应机制，相比于MgH，MgD的形成具有显著优势。在0.01至0.20 eV的碰撞能量范围内，MgD/MgH分支比从10.58单调下降至3.88，在0.114 eV的碰撞能量下，其接近5的实验值。两个通道的振转态分辨积分截面表明，产物MgD具有更高的振动激发和更热的转动态分布。不透明度函数P(J)表明，MgH + D通道和MgD + H通道分别由高b和低b碰撞主导。在微分截面曲线中发现了前向和后向散射峰，然而，由于反应中复合物的寿命较短，产物的角度分布并非严格的前后对称。
