Time-Resolved Femtosecond Photoelectron Spectroscopy by Field-Induced Surface Hopping

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• 作者：Roland Mitric虂 ; Jens Petersen ; Matthias Wohlgemuth ; Ute Werner ; Vlasta Bonac虒ic虂-Koutecky虂 ; Ludger Wo虉ste ; Joshua Jortner
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：April 28, 2011
• 年：2011
• 卷：115
• 期：16
• 页码：3755-3765
• 全文大小：1108K
• 年卷期：v.115,no.16(April 28, 2011)
• ISSN：1520-5215

文摘

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 鈥渙n the fly鈥?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 Ag₃, 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.