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Title: Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory

Abstract

With the help of newly developed X-ray free-electron laser (XFEL) sources, creating double core holes (DCHs) simultaneously at the same or different atomic sites in a molecule has now become possible. DCH X-ray emission is a new form of X-ray nonlinear spectroscopy that can be studied with a XFEL. Here in this paper, we computationally explore the metal K-edge valence-to-core (VtC) X-ray emission spectroscopy (XES) of metal/metal and metal/ligand DCH states in a series of transition metal complexes with time-dependent density functional theory. The simulated DCH VtC-XES signals are compared with conventional single core hole (SCH) XES signals. The energy shifts and intensity changes of the DCH emission lines with respect to the corresponding SCH-XES features are fingerprints of the coupling between the second core hole and the occupied orbitals around the DCHs that contain important chemical bonding information of the complex. The difference between delocalized/localized core hole models on DCH VtC-XES is also briefly discussed. We theoretically demonstrate that DCH XES provides subtle information on the local electronic structure around metal centers in transition metal complexes beyond conventional linear XES. In conclusion, our predicted changes from calculations between SCH-XES and DCH-XES features should be detectable with modern XFEL sources.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [5]
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford PULSE Inst.
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). LCLS and Stanford PULSE Inst.
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Univ. of Washington, Seattle, WA (United States)
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1591640
Alternate Identifier(s):
OSTI ID: 1570073
Grant/Contract Number:  
KC030105172685; SC0019277; AC05-76RL1830; AC02-76SF00515; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 14; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Yu, Bergmann, Uwe, Schoenlein, Robert, Khalil, Munira, and Govind, Niranjan. Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory. United States: N. p., 2019. Web. doi:10.1063/1.5111141.
Zhang, Yu, Bergmann, Uwe, Schoenlein, Robert, Khalil, Munira, & Govind, Niranjan. Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory. United States. doi:10.1063/1.5111141.
Zhang, Yu, Bergmann, Uwe, Schoenlein, Robert, Khalil, Munira, and Govind, Niranjan. Fri . "Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory". United States. doi:10.1063/1.5111141.
@article{osti_1591640,
title = {Double core hole valence-to-core x-ray emission spectroscopy: A theoretical exploration using time-dependent density functional theory},
author = {Zhang, Yu and Bergmann, Uwe and Schoenlein, Robert and Khalil, Munira and Govind, Niranjan},
abstractNote = {With the help of newly developed X-ray free-electron laser (XFEL) sources, creating double core holes (DCHs) simultaneously at the same or different atomic sites in a molecule has now become possible. DCH X-ray emission is a new form of X-ray nonlinear spectroscopy that can be studied with a XFEL. Here in this paper, we computationally explore the metal K-edge valence-to-core (VtC) X-ray emission spectroscopy (XES) of metal/metal and metal/ligand DCH states in a series of transition metal complexes with time-dependent density functional theory. The simulated DCH VtC-XES signals are compared with conventional single core hole (SCH) XES signals. The energy shifts and intensity changes of the DCH emission lines with respect to the corresponding SCH-XES features are fingerprints of the coupling between the second core hole and the occupied orbitals around the DCHs that contain important chemical bonding information of the complex. The difference between delocalized/localized core hole models on DCH VtC-XES is also briefly discussed. We theoretically demonstrate that DCH XES provides subtle information on the local electronic structure around metal centers in transition metal complexes beyond conventional linear XES. In conclusion, our predicted changes from calculations between SCH-XES and DCH-XES features should be detectable with modern XFEL sources.},
doi = {10.1063/1.5111141},
journal = {Journal of Chemical Physics},
number = 14,
volume = 151,
place = {United States},
year = {2019},
month = {10}
}

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