Time-resolved pump-probe spectroscopy to follow valence electronic motion in molecules: Theory
Time-resolved pump-probe spectroscopy to follow valence electronic motion in molecules: Theory
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时间分辨泵浦探针光谱跟踪分子中的价电子运动：理论
DOI：
10.1103/physreva.88.013419
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发表时间：
2013
影响因子：
2.9
通讯作者：
L. S. Cederbaum
中科院分区：
文献类型：
--
作者：
A. D. Dutoi;K. Gokhberg;L. S. Cederbaum
预计光子能量为几百eV到1 keV的阿秒脉冲的实验实现，我们已经开发了一种形式，使用单电子降密度算子将紫外线泵浦的非稳态电子状态的演变与x射线探测信号联系起来。我们希望跟踪的电子状态在几飞秒的时间尺度上演化，这些状态的价占比结构可以在空间和时间上探测和解决，通过利用核价跃迁的固有局部性和它们可以产生的相对较短的时间尺度。随时间变化的约化密度算符是一个直观简单的量，表示价能级的动态占有结构，但它对于任意多体态是很好的定义。本文概述了多体理论的复杂性与动态局部轨道占用的直观图像之间的联系。
Anticipating the experimental realization of attosecond pulses with photon energies of a few hundred eV to 1 keV, we have developed a formalism that connects the evolution of a UV-pumped nonstationary electronic state to an x-ray probe signal, using the one-electron reduced density operator. The electronic states we wish to follow evolve on time scales of a few femtoseconds, and the valence occupancy structure of these states can be probed, resolved in both space and time, by taking advantage of the inherent locality of core-valence transitions and the comparatively short time scale on which they can be produced. The time-dependent reduced density operator is an intuitively simple quantity, representing the dynamic occupancy structure of the valence levels, but it is well defined for an arbitrary many-body state. This article outlines the connection between the complexities of many-body theory and an intuitive picture of dynamic local orbital occupancy.