Revealing core-valence interactions in solution with femtosecond X-ray pump X-ray probe spectroscopy

Weakly, Robert B.; Liekhus-Schmaltz, Chelsea E.; Poulter, Benjamin I.; Biasin, Elisa; Alonso-Mori, Roberto; Aquila, Andrew; Boutet, Sébastien; Fuller, Franklin D.; Ho, Phay J.; Kroll, Thomas; Loe, Caroline M.; Lutman, Alberto; Zhu, Diling; Bergmann, Uwe; Schoenlein, Robert W.; Govind, Niranjan; Khalil, Munira

doi:10.1038/s41467-023-39165-2

Title: Revealing core-valence interactions in solution with femtosecond X-ray pump X-ray probe spectroscopy

Journal Article · 09 June 2023 · Nature Communications

DOI: https://doi.org/10.1038/s41467-023-39165-2 · OSTI ID:1984540

; Liekhus-Schmaltz, Chelsea E.;

;

; Fuller, Franklin D.;

; Kroll, Thomas; Loe, Caroline M.;

; Zhu, Diling;

;

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 1 s 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 1 s → 3 p 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 3 d with 3 p 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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)

Sponsoring Organization:: National Institute of General Medical Sciences (NIGMS); National Institutes of Health (NIH); National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC02-06CH11357; AC02-76SF00515; AC05-76RL01830; SC0019277; SC0023249

OSTI ID:: 1984540

Report Number(s):: PNNL-SA--182028; 3384; PII: 39165

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 14; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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Title: Revealing core-valence interactions in solution with femtosecond X-ray pump X-ray probe spectroscopy

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