论文标题
在非绝热动力学中的详细平衡:从旋转球到平衡椭圆形
On detailed balance in nonadiabatic dynamics: From spin spheres to equilibrium ellipsoids
论文作者
论文摘要
在多个量子电子状态上传播经典核的基于轨迹的方法通常用于模拟凝结相中的非绝热过程。这些方法的一个长期存在的问题是它们缺乏详细的平衡,这意味着它们不能保存平衡分布。在本文中,我们研究了如何通过调整以前提议的热平衡的旋转映射方法来恢复混合量子系统中详细平衡的想法。我们发现适应自旋幅度可以恢复正确的长期种群,但不足以保存完整的平衡分布。但是,可以通过将旋转更灵活地映射到椭圆形上来实现后者,该图的构造是为了实现任意电位的详细平衡。这种椭圆形的方法解决了困扰先前的映射方法的负人群的问题,因此也可以应用于强烈的不对称和非统计系统。由于它可以保存热分布,因此该方法还可以利用标准分子动力学中使用的有效采样方案,从而大大减少收敛所需的轨迹数量。但是,动力学确实具有均值场特征,正如通过评估黄金规则极限中的反应速率最清楚地观察到的。这意味着,尽管椭圆形映射提供了一个严格的框架,但需要进一步的工作才能找到准确的经典横向标记近似,该近似捕获了真正的量子动力学的更多属性。
Trajectory-based methods that propagate classical nuclei on multiple quantum electronic states are often used to simulate nonadiabatic processes in the condensed phase. A long-standing problem of these methods is their lack of detailed balance, meaning that they do not conserve the equilibrium distribution. In this article, we investigate ideas for how to restore detailed balance in mixed quantum--classical systems by tailoring the previously proposed spin-mapping approach to thermal equilibrium. We find that adapting the spin magnitude can recover the correct long-time populations but is insufficient to conserve the full equilibrium distribution. The latter can however be achieved by a more flexible mapping of the spin onto an ellipsoid, which is constructed to fulfill detailed balance for arbitrary potentials. This ellipsoid approach solves the problem of negative populations that has plagued previous mapping approaches and can therefore be applied also to strongly asymmetric and anharmonic systems. Because it conserves the thermal distribution, the method can also exploit efficient sampling schemes used in standard molecular dynamics, which drastically reduces the number of trajectories needed for convergence. The dynamics does however still have mean-field character, as is observed most clearly by evaluating reaction rates in the golden-rule limit. This implies that although the ellipsoid mapping provides a rigorous framework, further work is required to find an accurate classical-trajectory approximation that captures more properties of the true quantum dynamics.