论文标题

一种用于通过电子自旋建模非绝热核动力学的半经典方法

A Phase-Space Semiclassical Approach for Modeling Nonadiabatic Nuclear Dynamics with Electronic Spin

论文作者

Wu, Yanze, Bian, Xuezhi, Rawlinson, Jonathan, Littlejohn, Robert G., Subotnik, Joseph E.

论文摘要

化学松弛现象,包括光化学和电子传递过程,构成了一个剧烈的研究领域,在该领域中,非绝热动力学起着基本作用。在这里,我们表明,对于具有两个电子状态的非绝热动力学和不遵守时间反转对称性的复杂值的哈密顿量,最佳的半经典方法是在一组相位空间绝热表面上运行表面跳跃动力学。为了产生这种相位二下,必须隔离一组适当的糖尿病,并应用相规变换,然后最终将总哈密顿量对角线化(现在由R和P进行了参数化)。所得算法在绝热和非绝热限制中都是有效的,结合了所有浆果曲率效应,并允许在存在自旋轨道耦合和/或外部磁场的情况下研究半经典的非绝热动力学。

Chemical relaxation phenomena, including photochemistry and electron transfer processes, form a vigorous area of research in which nonadiabatic dynamics plays a fundamental role. Here, we show that for nonadiabatic dynamics with two electronic states and a complex-valued Hamiltonian that does not obey time-reversal symmetry, the optimal semiclassical approach is to run surface hopping dynamics on a set of phase-space adiabatic surfaces. In order to generate such phase-adiabats, one must isolate a proper set of diabats and apply a phase gauge transformation, before eventually diagonalizing the total Hamiltonian (which is now parameterized by both R and P). The resulting algorithm is valid in both the adiabatic and nonadiabatic limits, incorporates all Berry curvature effects, and allows for the study of semiclassical nonadiabatic dynamics in the presence of spin-orbit coupling and/or external magnetic fields.

扫码加入交流群

加入微信交流群

微信交流群二维码

扫码加入学术交流群,获取更多资源