Ab Initio Quasiclassical Simulation of Femtosecond Time-Resolved Two-Dimensional Electronic Spectra of Pyrazine.
Ab Initio Quasiclassical Simulation of Femtosecond Time-Resolved Two-Dimensional Electronic Spectra of Pyrazine.
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DOI：
10.1021/acs.jpclett.1c03589
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发表时间：
2021-12
期刊：
影响因子：
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通讯作者：
Xiang Huang;Weiwei Xie;N. Došlić;M. Gelin;W. Domcke
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文献类型：
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作者：
Xiang Huang;Weiwei Xie;N. Došlić;M. Gelin;W. Domcke
二维（2D）电子光谱是一种强大的非线性技术，其提供关于两个频率轴的光谱信息以及作为所谓的等待时间的函数的动力学信息。在这里，从头计算的理论框架，电子二维光谱的模拟已经发展。该方法基于三脉冲光子回波信号的门口窗口表示的经典近似和经典轨迹对核运动的描述。考虑到非绝热效应的轨迹表面跳跃算法。二维电子光谱是通过使用ADC（2）电子结构方法的吡嗪分子的从头算飞行轨道计算来模拟的，吡嗪分子是通过圆锥相交的超快无辐射衰变的基准系统。它表明，二维光谱与亚飞秒紫外脉冲可以提供前所未有的详细信息的超快多原子分子的光动力学。
Two-dimensional (2D) electronic spectroscopy is a powerful nonlinear technique which provides spectroscopic information on two frequency axes as well as dynamical information as a function of the so-called waiting time. Herein, an ab initio theoretical framework for the simulation of electronic 2D spectra has been developed. The method is based on the classical approximation to the doorway-window representation of three-pulse photon-echo signals and the description of nuclear motion by classical trajectories. Nonadiabatic effects are taken into account by a trajectory surface-hopping algorithm. 2D electronic spectra were simulated with ab initio on-the-fly trajectory calculations using the ADC(2) electronic-structure method for the pyrazine molecule, which is a benchmark system for ultrafast radiationless decay through conical intersections. It is demonstrated that 2D spectroscopy with subfemtosecond UV pulses can provide unprecedented detailed information on the ultrafast photodynamics of polyatomic molecules.