Yang Zijiang, Yuan Jiuchuang, Wang Shufen, 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 P. R. China
RSC Adv. 2018 Jun 21;8(40):22823-22834. doi: 10.1039/c8ra04305a. eCollection 2018 Jun 19.
The Be(P) + H(XΣ ) → BeH(XΣ) + H(S) reaction has great significance for studying diabatic processes and ultracold chemistry. The first global diabatic potential energy surfaces (PESs) which are correlated with the lowest two adiabatic states 1A' and 2A' of the BeH system are constructed by using the neural network method. energy points are calculated using the multi-reference configuration interaction method with the Davidson correction and AVQZ basis set. The diabatic energies are obtained from the transformation of data based on the dipole moment operators. The topographical characteristics of the diabatic PESs are described in detail, and the positions of crossing between the and are pinpointed. On new diabatic PESs, the time-dependent quantum wave packet method is carried out to study the mechanism of the title reaction. The results of dynamics calculations indicate the reaction has no threshold and the product BeH is excited to high vibrational states easily. In addition, the product BeH tends to backward scattering at most collision energies.
Be(P) + H(XΣ ) → BeH(XΣ) + H(S)反应对于研究非绝热过程和超冷化学具有重要意义。利用神经网络方法构建了与BeH体系最低两个绝热态1A'和2A'相关的首个全局非绝热势能面（PESs）。使用带有戴维森校正的多参考组态相互作用方法和AVQZ基组计算能量点。非绝热能量通过基于偶极矩算符的数据变换获得。详细描述了非绝热PESs的地形特征，并确定了它们之间交叉的位置。在新的非绝热PESs上，采用含时量子波包方法研究了上述反应机理。动力学计算结果表明该反应无阈值，产物BeH很容易被激发到高振动态。此外，在大多数碰撞能量下，产物BeH倾向于向后散射。
