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author Rivas, Daniel E.
Paoloni, Lorenzo
Boll, Rebecca
De Fanis, Alberto
Gutiérrez, Ana Martínez
Mazza, Tommaso
Oberli, Solène
Alexander, Oliver
Al-Haddad, André
Baumann, Thomas M.
Bostedt, Christoph
Dold, Simon
Geloni, Gianluca
Ilchen, Markus
Moonshiram, Dooshaye
Rolles, Daniel
Rudenko, Artem
Schmidt, Philipp
Serkez, Svitozar
Usenko, Sergey
Pendás, Ángel Martín
Meyer, Michael
González-Vázquez, Jesús
Picón, Antonio
author_facet Rivas, Daniel E.
Paoloni, Lorenzo
Boll, Rebecca
De Fanis, Alberto
Gutiérrez, Ana Martínez
Mazza, Tommaso
Oberli, Solène
Alexander, Oliver
Al-Haddad, André
Baumann, Thomas M.
Bostedt, Christoph
Dold, Simon
Geloni, Gianluca
Ilchen, Markus
Moonshiram, Dooshaye
Rolles, Daniel
Rudenko, Artem
Schmidt, Philipp
Serkez, Svitozar
Usenko, Sergey
Pendás, Ángel Martín
Meyer, Michael
González-Vázquez, Jesús
Picón, Antonio
contents Traditional x-ray photoelectron spectroscopy (XPS) relies upon a direct mapping between the photoelectron binding energies and the local chemical environment, which is well-characterized by an electrostatic partial charges model for systems in equilibrium. However, the extension of this technique to out-of-equilibrium systems has been hampered by the lack of x-ray sources capable of accessing multiple atomic sites with high spectral and temporal resolution, as well as the lack of simple theoretical procedures to interpret the observed signals. In this work we employ multi-site XPS with a narrowband femtosecond x-ray probe to unravel different ultrafast dissociation processes of a polyatomic molecule, fluoromethane (CH$_{3}$F). We show that XPS can follow the cleavage of both the C-F and C-H bonds in real time, despite these channels lying close in binding energy. Additionally, we apply the partial charges model to describe these dynamics, and verify this extension with both advanced ab-initio calculations and experimental data. These results enable the application of this technique to out-of-equilibrium systems of higher complexity, by correlating real-time information from multiple atomic sites and interpreting the measurements through a viable theoretical modelling.
format Preprint
id arxiv_https___arxiv_org_abs_2512_13079
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Unraveling real-time chemical shifts in the ultrafast regime
Rivas, Daniel E.
Paoloni, Lorenzo
Boll, Rebecca
De Fanis, Alberto
Gutiérrez, Ana Martínez
Mazza, Tommaso
Oberli, Solène
Alexander, Oliver
Al-Haddad, André
Baumann, Thomas M.
Bostedt, Christoph
Dold, Simon
Geloni, Gianluca
Ilchen, Markus
Moonshiram, Dooshaye
Rolles, Daniel
Rudenko, Artem
Schmidt, Philipp
Serkez, Svitozar
Usenko, Sergey
Pendás, Ángel Martín
Meyer, Michael
González-Vázquez, Jesús
Picón, Antonio
Chemical Physics
Optics
Quantum Physics
Traditional x-ray photoelectron spectroscopy (XPS) relies upon a direct mapping between the photoelectron binding energies and the local chemical environment, which is well-characterized by an electrostatic partial charges model for systems in equilibrium. However, the extension of this technique to out-of-equilibrium systems has been hampered by the lack of x-ray sources capable of accessing multiple atomic sites with high spectral and temporal resolution, as well as the lack of simple theoretical procedures to interpret the observed signals. In this work we employ multi-site XPS with a narrowband femtosecond x-ray probe to unravel different ultrafast dissociation processes of a polyatomic molecule, fluoromethane (CH$_{3}$F). We show that XPS can follow the cleavage of both the C-F and C-H bonds in real time, despite these channels lying close in binding energy. Additionally, we apply the partial charges model to describe these dynamics, and verify this extension with both advanced ab-initio calculations and experimental data. These results enable the application of this technique to out-of-equilibrium systems of higher complexity, by correlating real-time information from multiple atomic sites and interpreting the measurements through a viable theoretical modelling.
title Unraveling real-time chemical shifts in the ultrafast regime
topic Chemical Physics
Optics
Quantum Physics
url https://arxiv.org/abs/2512.13079