Time-resolved Intramolecular Photoelectron Diffraction (TIPD) of Ions in the Gas-phase

能够在原子运动的时间尺度(飞秒)上探测结构(电子和几何)变化为理解化学中的结构-功能关系提供了最直接的途径，而化学是许多现代技术的基础。在这里，我们提出了一种新的概念上的方法，时间分辨分子内光电子衍射(TIPD)，在这种方法中，光电子从质量选择的气相聚阴离子中的带负电荷的官能团中衍射出来。测量的干涉图包含关于电荷位置相对于电子脱离的分子轨道的位置的结构信息。它可以在低于100 fs的分辨率下测量，从而能够实时探测光诱导过程，包括蛋白质和导电聚合物中的电荷转移过程和结构转变。

Being able to probe structural (electronic and geometric) change on the timescale of atomic motion(femtoseconds) offers the most direct route to understanding the structure-function relationship inchemistry, which underpins much of modern technology. Here, we propose the conceptually novelmethod, Time-resolved Intramolecular Photoelectron Diffraction (TIPD), in which photoelectrons arediffracted from negatively-charged functional groups in a mass-selected gas-phase polyanion. Themeasured interferogram contains structural information about the location of charge-sites relative tothe molecular orbital from which an electron is detached. It can be measured with sub-100 fsresolution to enable real-time probing of photoinduced processes including charge-transferprocesses and structural transformations in, for example, proteins and conducting polymers.