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

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. A.; Gühr, M.

doi:10.1038/s41467-021-27908-y

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

Journal Article · Tue Jan 11 00:00:00 EST 2022 · Nature Communications

DOI:https://doi.org/10.1038/s41467-021-27908-y· OSTI ID:1862324

^[1]; ^[1]; ^[1]; Metje, J. ^[1]; ^[2]; ^[3]; ^[2]; ^[4]; Feifel, R. ^[5]; ^[1]; ^[2]; Kuhlmann, M. ^[2]; Mazza, T. ^[6]; Robinson, M. S. ^[7]; Squibb, R. J. ^[5]; ^[2]; Wallner, M. ^[5]; Saalfrank, P. ^[1]; ^[8]; Gühr, M. ^[1]

Univ. of Potsdam (Germany)
Deutsches Elektronen Synchrotron (DESY), Hamburg (Germany)
Deutsches Elektronen Synchrotron (DESY), Hamburg (Germany); Univ. of Hamburg (Germany)
Heidelberg Institute for Theoretical Studies (Germany)
Univ. of Gothenburg (Sweden)
European XFEL, Schenefeld (Germany)
Univ. of Potsdam (Germany); Deutsches Elektronen Synchrotron (DESY), Hamburg (Germany); Univ. of Hamburg (Germany)
SLAC National Accelerator Lab., Menlo Park, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: European Research Council; Federal Ministry of Education and Research (BMBF); German Research Foundation (DFG); Knut and Alice Wallenberg Foundation; Swedish Research Council; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1862324

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 13; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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