Time-resolved femtosecond photoelectron spectroscopy by field-induced surface hopping.
Time-resolved femtosecond photoelectron spectroscopy by field-induced surface hopping.
复制标题
通过场诱导表面跳跃的时间分辨飞秒光电子能谱。
DOI：
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发表时间：
2011
影响因子：
2.9
通讯作者：
J. Jortner
中科院分区：
文献类型：
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作者：
R. Mitrić;J. Petersen;Matthias Wohlgemuth;U. Werner;V. Bonačić‐Koutecký;L. Wöste;J. Jortner
本文将场致表面跳跃方法推广到光电离过程的描述和时间分辨光电子谱的模拟。这是基于非绝热分子动力学的组合“在飞”的TDDFT的框架下广义的开壳层系统的影响下的激光场与近似的量子力学描述的光电离过程。由于可以采用任意的脉冲形状，这种方法也可以与最优控制理论相结合，以控制光电离或塑造输出的电子波包。我们说明了我们的方法模拟TRPES的原型系统的Ag（3），其中包括激发从平衡三角形的几何形状，以及激发从线性过渡态，在这两种情况下，非绝热弛豫发生在一个复杂的歧管的电子状态。我们的方法代表了一个普遍适用的方法预测的时间分辨光电子能谱和分析系统具有复杂的电子结构，以及许多核自由度。这一理论发展应有助于激发新的超快实验。
We present the extension of our field-induced surface hopping method for the description of the photoionization process and the simulation of time-resolved photoelectron spectra (TRPES). This is based on the combination of nonadiabatic molecular dynamics "on the fly" in the framework of TDDFT generalized for open shell systems under the influence of laser fields with the approximate quantum mechanical description of the photoionization process. Since arbitrary pulse shapes can be employed, this method can be also combined with the optimal control theory in order to steer the photoionization or to shape the outgoing electronic wavepackets. We illustrate our method for the simulation of TRPES on the prototype system of Ag(3), which involves excitation from the equilibrium triangular geometry, as well as excitation from the linear transition state, where in both cases nonadiabatic relaxation takes place in a complex manifold of electronic states. Our approach represents a generally applicable method for the prediction of time-resolved photoelectron spectra and their analysis in systems with complex electronic structure as well as many nuclear degrees freedom. This theoretical development should serve to stimulate new ultrafast experiments.