Department of Physics , Imperial College London , Prince Consort Road , London SW7 2AZ , United Kingdom.
Dipartimento di Scienze Chimiche , Università di Trieste , Via Giorgieri 1 , I-34127 Trieste , Italy.
J Chem Theory Comput. 2018 Oct 9;14(10):4991-5000. doi: 10.1021/acs.jctc.8b00479. Epub 2018 Sep 18.
Here, we present an ab initio approach to full simulation of an attosecond molecular pump-probe experiment. Sequential molecular double ionization by the pump and probe laser pulses with controlled delay is described from first-principles with a full account of the continuum dynamics of the photoelectrons. Many-electron bound-continuum dynamics is simulated using the time-dependent (TD) molecular B-spline algebraic diagrammatic construction (ADC) method. Our calculations give a quantitative prediction about the creation of a coherent superposition of molecular ionic states in the photoionization process and simulate the probe of the ensuing attosecond dynamics by a second ionizing pulse within a single first-principles many-electron framework. We therefore demonstrate the capability to simulate and interpret the results of a prototypical molecular pump-probe experiment of interest in attoscience. As a particular example, we simulate and elucidate the interpretation of a pump-probe experiment in CO aimed at measuring strong field-induced hole dynamics via photoionization yields.
在这里，我们提出了一种从头算方法，用于对阿秒分子泵浦探测实验进行全模拟。通过泵浦和探测激光脉冲的顺序分子双电离，我们从第一性原理出发，并充分考虑光电子的连续动力学，对其进行了控制延迟的描述。使用含时（TD）分子 B 样条代数图构造（ADC）方法对多电子束缚-连续动力学进行了模拟。我们的计算对光离过程中分子离子态相干叠加的产生给出了定量预测，并在单个多电子从头算框架内用第二个电离脉冲模拟了随后的阿秒动力学的探测。因此，我们证明了在阿秒科学中模拟和解释典型分子泵浦探测实验结果的能力。作为一个特定的例子，我们模拟并阐明了 CO 中泵浦探测实验的解释，该实验旨在通过光离产额测量强场诱导的空穴动力学。
