Photoinduced Enhancement of Chemical Shift Sensitivity to Local Vibrations
Abstract
Abstract The advent of novel free-electron laser sources enabling time-resolved X-ray photoelectron spectroscopy (tr-XPS) provides a unique opportunity to monitor local chemical environments in real time by measuring sub-eV shifts in core-electron binding energies. These shifts reflect the interplay between electronic excitation and nuclear motion, an interplay that remains largely unexplored. In our combined theoretical and experimental study of fluoropyridine (C5H4FN), we investigate this link by monitoring the evolving chemical environment at the N and F atomic sites as the photoexcited S1 state relaxes to the ground state via a conical intersection. We find that the F site responds primarily to vibrational relaxation, showing minimal sensitivity to the electronic excited state. In contrast, excitation to S1 induces a measurable energy shift at the N site and significantly enhances its sensitivity to local vibrations within the ring. This behavior arises from a photoinduced redistribution of charge, which also increases the Coulomb interaction between the 1s electron at the N atom and the atomic partial charge at an adjacent C atom. This insight opens new avenues for exploring ultrafast dynamics and conical intersection pathways in more complex systems, from photostable DNA bases to light-harvesting materials.
Article Details
Journal Info
Journal of the American Chemical Society
American Chemical Society
Authors (29)
Ana Martínez Gutiérrez
Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC) , ,
Oliver Alexander
Imperial College London , , ,
Pablo Estévez Alonso
Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC) , ,
Lorenzo Paoloni
Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC) , ,
Terry Mullins
European XFEL , Holzkoppel 4 , ,
Andre Al-Haddad
Thomas M. Baumann
Rebecca Boll
European XFEL , Holzkoppel 4 , ,
Christoph Bostedt
Simon Dold
European XFEL , Holzkoppel 4 , ,
Alberto De Fanis
Gianluca Geloni
European XFEL , Holzkoppel 4 , ,
Markus Ilchen
Deutsches Elektronen-Synchrotron DESY , Notkestr. 85 , ,
Iyas Ismail
CNRS, UMR 7614, Sorbonne Université , , 4 Place Jussieu , ,
Björn Lautenschlager
European XFEL , Holzkoppel 4 , ,
Tommaso Mazza
Dooshaye Moonshiram
Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC) , ,
Solène Oberli
École Polytechnique Fédérale de Lausanne (EPFL) , , ,
Dawei Peng
CNRS, UMR 7614, Sorbonne Université , , 4 Place Jussieu , ,
Ralph Püttner
Freie Universität Berlin , , Arnimallee 14 , ,
Svitozar Serkez
European XFEL , Holzkoppel 4 , ,
Marc Simon
Florian Trinter
Fritz-Haber-Institut der Max-Planck-Gesellschaft , , Faradayweg 4-6 , ,
Sergey Usenko
Michael Meyer
Jonathan P. Marangos
Imperial College London , , ,
Jesús González-Vázquez
Universidad Autónoma de Madrid , , ,
Daniel E. Rivas
European XFEL , Holzkoppel 4 , ,
Antonio Picón
Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas (ICMM-CSIC) , ,