Revealing core-valence interactions in solution with femtosecond X-ray pump X-ray probe spectroscopy
Year: 2023
Type: article
Abstract: Femtosecond pump-probe spectroscopy using ultrafast optical and infrared pulses has become an essential tool to discover and understand complex electronic and structural dynamics in solvated molecular, biological, and material systems. Here we report the experimental realization of an ultrafast two-color X-ray pump X-ray probe transient absorption experiment performed in solution. A 10 fs X-ray pump pulse creates a localized excitation by removing a 1s electron from an Fe atom in solvated ferro- and ferricyanide complexes. Following the ensuing Auger-Meitner cascade, the second X-ray pulse probes the Fe 1s → 3p transitions in resultant novel core-excited electronic states. Careful comparison of the experimental spectra with theory, extracts +2 eV shifts in transition energies per valence hole, providing insight into correlated interactions of valence 3d with 3p and deeper-lying electrons. Such information is essential for accurate modeling and predictive synthesis of transition metal complexes relevant for applications ranging from catalysis to information storage technology. This study demonstrates the experimental realization of the scientific opportunities possible with the continued development of multicolor multi-pulse X-ray spectroscopy to study electronic correlations in complex condensed phase systems.
Source: Nature Communications
Authors: Robert B. Weakly, Chelsea E. Liekhus-Schmaltz, Benjamin I. Poulter, Elisa Biasin, Roberto Alonso-Mori, Andrew Aquila, Sébastien Boutet, Franklin D. Fuller, Phay J. Ho, Thomas Kroll, Caroline M. Loe, Alberto Lutman, Diling Zhu, Uwe Bergmann, Robert W. Schoenlein, Niranjan Govind, Munira Khalil
Language: English
Subfield: Radiation
Field: Physics and Astronomy
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $6,290
Funders: National Science Foundation, U.S. Department of Energy, Battelle, National Institutes of Health, Office of Science, National Institute of General Medical Sciences, Basic Energy Sciences, Biological and Environmental Research, Pacific Northwest National Laboratory, SLAC National Accelerator Laboratory
Awards: G102163711, G1229526393, G1286251239, G1804828992, G1831385526, G2287611682, G2371548206, G2393997808, G2558603588, G262532246, G262962599, G2738590184, G2857925935, G2988778103, G2994398150, G2998698001, PROBING AND CONTROLLING ELECTRONIC CORRELATIONS AND VIBRONIC COUPLING DURING ULTRAFAST INTRAMOLECULAR ELECTRON TRANSFER IN SOLVATED MIXED VALENCE COMPLEXES, G303061748, G315621713, G3488436650, G3606907272, G3629260272, G3688579682, G409777406, G4235786860, G426311843, G4269941704, G4280418065, G440375865, Graduate Research Fellowship Program (GRFP), G4581610328, G4908923434, G495301720, G498139845, G513797252, G5387317844, G5570207115, G5607048534, G5726405315, FEMTOSECOND X-RAY PROBES OF COHERENCE IN ULTRAFAST PHOTOINDUCED ELECTRON AND PROTON TRANSFERS, G6224570086, G628751139, G6550344761, G6597962636, G6848031779, G6918803902, G7083997402, G7210414935, G7283024673, G7313278570, G7396808078, G7583137537, PROBING AND CONTROLLING ELECTRONIC CORRELATIONS AND VIBRONIC COUPLING DURING ULTRAFAST INTRAMOLECULAR ELECTRON TRANSFER IN SOLVATED MIXED VALENCE COMPLEXES, G7863156295, G8382000481, A Synchrotron Radiation Structural Biology Resource, G8925327636, A Synchrotron Radiation Structural Biology Resource, G911061179, G969889393, G993149817
OpenAlex ID: W4379967243