Freie Universität Berlin, Fachbereich Physik, Arnimallee 14, D-14195 Berlin, Germany.
Phys Chem Chem Phys. 2011 May 21;13(19):8690-6. doi: 10.1039/c0cp02935a. Epub 2011 Apr 11.
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.
我们呈现了涉及从线性过渡态激发的 Ag(3) 的时间分辨光电子能谱的模拟，其中非绝热弛豫发生在复杂的电子态流形中。因此，我们从线性 Ag 阴离子物种出发，研究了通过负离子到中性到正离子（NeNePo）光谱可达到的超快过程。为此，我们使用了我们新开发的场诱导表面跳跃方法（FISH）来描述光电离过程。此外，我们在时间相关密度泛函理论的框架内，针对开壳系统进行非绝热分子动力学的“实时”模拟。我们提出的方法通常适用于预测具有复杂电子结构和多个核自由度的系统中的时间分辨光电子能谱及其分析。这一理论发展应该有助于激发新的超快实验。
