Field-induced surface hopping method for probing transition state nonadiabatic dynamics of Ag3.
Field-induced surface hopping method for probing transition state nonadiabatic dynamics of Ag3.
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用于探测 Ag3 过渡态非绝热动力学的场诱导表面跳跃方法。
DOI：
10.1039/c0cp02935a
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
V. Bonačić‐Koutecký
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
我们提出了Ag(3)的时间分辨光电子能谱的模拟，涉及从线性过渡态激发，其中非绝热弛豫发生在复杂的电子态流形中。因此，我们解决了从线性银阴离子物种开始的负离子到中性到正离子（NeNePo）光谱可达到的超快过程。为此，我们采用了新开发的场致表面跳变法（FISH）来描述光电离过程。此外，我们将非绝热分子动力学的方法应用于开壳系统的时变密度泛函理论的框架中。本文提出的方法一般适用于具有复杂电子结构和多核自由度系统的时间分辨光电子能谱的预测和分析。这一理论的发展将有助于激发新的超快实验。
We present the simulation of time-resolved photoelectron spectra of Ag(3) involving excitation from the linear transition state, where nonadiabatic relaxation takes place in a complex manifold of electronic states. Thus, we address ultrafast processes reachable by negative ion-to neutral-to positive ion (NeNePo) spectroscopy starting from the linear Ag anionic species. For this purpose we use our newly developed field-induced surface hopping method (FISH) augmented for the description of photoionization processes. Furthermore we employ our method for nonadiabatic molecular dynamics "on the fly" in the framework of time-dependent density functional theory generalized for open shell systems. Our presented approach is generally applicable 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.