Conservation of Angular Momentum in Direct Nonadiabatic Dynamics
Conservation of Angular Momentum in Direct Nonadiabatic Dynamics
复制标题
直接非绝热动力学中角动量守恒
DOI：
10.1021/acs.jpclett.9b03749
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发表时间：
2020
影响因子：
5.7
通讯作者：
Truhlar Donald G.
中科院分区：
文献类型：
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作者：
Shu Yinan;Zhang Linyao;Varga Zoltan;Parker Kelsey A.;Kanchanakungwankul Siriluk;Sun Shaozeng;Truhlar Donald G.
直接非绝热动力学用于研究涉及从小分子到材料的多种电子态的过程。与拟合分析势能面的动力学相比，直接动力学更加用户友好，因为它通过电子结构计算获得所有所需的能量、梯度和非绝热耦合（NAC）。然而，在广泛使用的混合量子经典非绝热动力学算法中，通常使用的 NAC 不守恒角动量或质心，特别是轨迹表面跳跃、半经典 Ehrenfest 和混合衰减的相干切换。我们证明，通过使用投影算子去除最初计算的 NAC 的平移和旋转分量，可以恢复守恒。
Direct nonadiabatic dynamics is used to study processes involving multiple electronic states from small molecules to materials. Compared with dynamics with fitted analytical potential energy surfaces, direct dynamics is more user-friendly in that it obtains all needed energies, gradients, and nonadiabatic couplings (NACs) by electronic structure calculations. However, the NAC that is usually used does not conserve angular momentum or the center of mass in widely used mixed quantum-classical nonadiabatic dynamics algorithms, in particular, trajectory surface hopping, semiclassical Ehrenfest, and coherent switching with decay of mixing. We show that by using a projection operator to remove the translational and rotational components of the originally computed NAC, one can restore the conservation.