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

能够探测原子运动时间尺度（飞秒）上的结构（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，这是现代技术的基础。在这里，我们提出了概念新颖的方法，时间分辨分子内光电子衍射（TIPD），其中光电子衍射从带负电荷的官能团在质量选择气相聚阴离子。测得的干涉图包含了关于电荷位置相对于电子脱离的分子轨道的结构信息。它可以以低于100 fs的分辨率进行测量，以便能够实时探测光诱导过程，包括电荷转移过程和结构转换，例如蛋白质和导电聚合物。

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.