TY  - JOUR
A1  - Mayer, Dennis
A1  - Lever, Fabiano
A1  - Picconi, David
A1  - Metje, Jan
A1  - Ališauskas, Skirmantas
A1  - Calegari, Francesca
A1  - Düsterer, Stefan
A1  - Ehlert, Christopher
A1  - Feifel, Raimund
A1  - Niebuhr, Mario
A1  - Manschwetus, Bastian
A1  - Kuhlmann, Marion
A1  - Mazza, Tommaso
A1  - Robinson, Matthew Scott
A1  - Squibb, Richard J.
A1  - Trabattoni, Andrea
A1  - Wallner, Måns
A1  - Saalfrank, Peter
A1  - Wolf, Thomas J. A.
A1  - Gühr, Markus
T1  - Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy
T2  - Nature communications
N2  - Imaging the charge flow in photoexcited molecules would provide key information on photophysical and photochemical processes. Here the authors demonstrate tracking in real time after photoexcitation the change in charge density at a specific site of 2-thiouracil using time-resolved X-ray photoelectron spectroscopy. The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220-250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states.
Y1  - 2022
UR  - https://publishup.uni-potsdam.de/frontdoor/index/index/docId/64202
SN  - 2041-1723
N1  - Publisher correction: https://doi.org/10.1038/s41467-022-28584-2
VL  - 13
IS  - 1
PB  - Nature Research
CY  - Berlin
ER  -