Ultrafast metal-to-ligand charge transfer driven by bond shortening revealed with dual-edge computational X-ray spectroscopy

Ultrafast metal-to-ligand charge transfer driven by bond shortening revealed with dual-edge computational X-ray spectroscopy | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Ultrafast metal-to-ligand charge transfer driven by bond shortening revealed with dual-edge computational X-ray spectroscopy Weijie Hua, Sheng-Yu Wang, Jun-Rong Zhang, Guoyan Ge This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7863223/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted You are reading this latest preprint version Abstract Understanding electron flow during chemical reactions is fundamental to ultrafast chemistry, particularly in transition metal complexes where redox processes involve intricate coupling between electronic and nuclear dynamics. While time-resolved X-ray spectroscopy provides a window into these dynamics, interpreting spectral data to identify transient intermediates and charge transfer mechanisms remains challenging. Here, we introduce a dual-edge computational spectroscopy approach that simultaneously simulates O K-edge and Cu L-edge X-ray absorption spectra for the paradigmatic CuO 2 + system. We show that symmetric Cu--O bond shortening drives the ultrafast conversion from Cu(I):O 2 to Cu(II):O 2 ∙- through metal-to-ligand charge transfer. Our peak-by-peak analysis along the binding coordinate directly resolves concurrent dioxygen reduction and copper oxidation, leveraging the interpretable ligand-centered O K-edge to decode the complex metal-centered L-edge spectrum. This work establishes a general protocol for extracting atomic-level electron flow from ultrafast X-ray spectra, with implications for metalloenzyme function, catalysis, and energy conversion. Physical sciences/Chemistry/Theoretical chemistry/Quantum chemistry Physical sciences/Physics/Atomic and molecular physics/Electronic structure of atoms and molecules Physical sciences/Chemistry/Inorganic chemistry/Chemical bonding Physical sciences/Optics and photonics/Optical physics/X-rays Full Text Additional Declarations There is NO Competing Interest. Supplementary Files siWangnc.pdf Supplementary Information Cite Share Download PDF Status: Under Review Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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