Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy

Abstract:

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.

SEEK ID: https://publications.h-its.org/publications/1574

DOI: 10.1038/s41467-021-27908-y

Research Groups: Computational Carbon Chemistry

Publication type: Journal

Journal: Nature Communications

Citation: Nat Commun 13(1),198

Date Published: 1st Dec 2022

Registered Mode: by DOI

Authors: D. Mayer, F. Lever, D. Picconi, J. Metje, S. Alisauskas, F. Calegari, S. Düsterer, C. Ehlert, R. Feifel, M. Niebuhr, B. Manschwetus, M. Kuhlmann, T. Mazza, M. S. Robinson, R. J. Squibb, A. Trabattoni, M. Wallner, P. Saalfrank, T. J. A. Wolf, M. Gühr

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Citation
Mayer, D., Lever, F., Picconi, D., Metje, J., Alisauskas, S., Calegari, F., Düsterer, S., Ehlert, C., Feifel, R., Niebuhr, M., Manschwetus, B., Kuhlmann, M., Mazza, T., Robinson, M. S., Squibb, R. J., Trabattoni, A., Wallner, M., Saalfrank, P., Wolf, T. J. A., & Gühr, M. (2022). Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy. In Nature Communications (Vol. 13, Issue 1). Springer Science and Business Media LLC. https://doi.org/10.1038/s41467-021-27908-y
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Created: 3rd Feb 2023 at 15:30

Last updated: 5th Mar 2024 at 21:25

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