Huang Jiayu, Zhang Dong H
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Science, Dalian 116023, China.
J Chem Phys. 2020 Oct 14;153(14):141102. doi: 10.1063/5.0028035.
We present a new approach to incorporate the geometric phase in the time-dependent wave packet calculations based on the analytic diabatic potential energy matrices for two-state systems connecting via a conical intersection. The approach only requires information on the location of the conical intersection and the adiabatic potential energy surface of the ground electronic state and merely takes the same computational cost as a diabatic calculation. Demonstrations of the benchmark H + H/HD reactions show that the new approach can accurately include the geometric phase in dynamics calculation and can be easily extended to the cold regime where the GP effects become more pronounced. Due to its simplicity and numerical efficiency, the new approach has the potential to extend the dynamics study of the geometric effects to a wide range of reaction systems.
我们提出了一种新方法，用于在基于通过锥形交叉连接的两态系统的解析非绝热势能矩阵的含时波包计算中纳入几何相位。该方法仅需要关于锥形交叉位置和基态电子态的绝热势能面的信息，并且计算成本仅与非绝热计算相同。基准H + H/HD反应的演示表明，新方法可以在动力学计算中准确纳入几何相位，并且可以轻松扩展到几何相位效应更显著的低温区域。由于其简单性和数值效率，新方法有潜力将几何效应的动力学研究扩展到广泛的反应系统。
