Origin of core-to-core x-ray emission spectroscopy sensitivity to structural dynamics

Vacher, Morgane; Kunnus, Kristjan; Delcey, Mickaël G.; Gaffney, Kelly J.; Lundberg, Marcus

doi:10.1063/4.0000022

Origin of core-to-core x-ray emission spectroscopy sensitivity to structural dynamics

Journal Article · Mon Jul 06 04:00:00 EDT 2020 · Structural Dynamics

DOI:https://doi.org/10.1063/4.0000022· OSTI ID:1656739

^[1]; ^[2]; Delcey, Mickaël G. ^[3]; ^[4]; ^[3]

Uppsala Univ. (Sweden); Centre National de la Recherche Scientifique (CNRS), Nantes (France). Univ. de Nantes
SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Univ. of Tartu (Estonia)
Uppsala Univ. (Sweden)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)

Recently, coherent structural dynamics in the excited state of an iron photosensitizer was observed through oscillations in the intensity of Kα x-ray emission spectroscopy (XES). Understanding the origin of the unexpected sensitivity of core-to-core transitions to structural dynamics is important for further development of femtosecond time-resolved XES methods and, we believe, generally necessary for interpretation of XES signals from highly non-equilibrium structures that are ubiquitous in photophysics and photochemistry. Here, we use multiconfigurational wavefunction calculations combined with atomic theory to analyze the emission process in detail. The sensitivity of core-to-core transitions to structural dynamics is due to a shift of the minimum energy metal–ligand bond distance between 1s and 2p core-hole states. A key effect is the additional contraction of the non-bonding 3s and 3p orbitals in 1s core-hole states, which decreases electron– electron repulsion and increases overlap in the metal–ligand bonds. The effect is believed to be general and especially pronounced for systems with strong bonds. The important role of 3s and 3p orbitals is consistent with the analysis of radial charge and spin densities and can be connected to the negative chemical shift observed for many transition metal complexes. The XES sensitivity to structural dynamics can be optimized by tuning the emission energy spectrometer, with oscillations up to ±4% of the maximum intensity for the current system. The theoretical predictions can be used to design experiments that separate electronic and nuclear degrees of freedom in ultrafast excited state dynamics.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Lab., Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; Knut and Alice Wallenberg Foundation; Foundation Olle Engkvist Byggmastare; Linkoping University; European Regional Development Fund

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1656739

Journal Information:: Structural Dynamics, Journal Name: Structural Dynamics Journal Issue: 4 Vol. 7; ISSN 2329-7778

Publisher:: American Crystallographic Association/AIPCopyright Statement

Country of Publication:: United States

Language:: English

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Origin of core-to-core x-ray emission spectroscopy sensitivity to structural dynamics

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