论文标题
多原子分子中电子相干的有效半经典评估
Efficient Semiclassical Evaluation of Electronic Coherences in Polyatomic Molecules
论文作者
论文摘要
暴露于强烈的光脉冲可能会使该分子进入非平稳量子状态，从而引发电子和核子系统的相关动力学。尽管在理解电子核相互作用和动力学背后的基本物理学方面已经实现了很多，但是在多原子分子中发生的光诱导过程的准确数值模拟仍然是一个巨大的挑战。在这里，我们回顾了一种最近开发的理论方法，用于评估分子中的电子相干，其中超快电子动力学与核运动耦合。提出的技术结合了对电子结构的准确拟合模拟与有效的半经典程序，以计算核波数据包的动力学，不仅在计算上有效，而且还可以帮助阐明基本的物理机制，使核重置的电子耦合型和电子耦合的复兴。
Exposing a molecule to intense light pulses may bring this molecule to a nonstationary quantum state, thus launching correlated dynamics of electronic and nuclear subsystems. Although much had been achieved in the understanding of fundamental physics behind the electron-nuclear interactions and dynamics, accurate numerical simulations of light-induced processes taking place in polyatomic molecules remain a formidable challenge. Here, we review a recently developed theoretical approach for evaluating electronic coherences in molecules, in which the ultrafast electronic dynamics is coupled to nuclear motion. The presented technique, which combines accurate ab initio on-the-fly simulations of electronic structure with efficient semiclassical procedure to compute the dynamics of nuclear wave packets, is not only computationally efficient, but also can help shed light on the underlying physical mechanisms of decoherence and revival of the electronic coherences driven by nuclear rearrangement.
