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Zinc 1s Valence-to-Core X-ray Emission Spectroscopy of Halozincate Complexes

Clarke, Coby J.; Hayama, Shusaku; Hawes, Alexander; Hallett, Jason P.; Chamberlain, Thomas W.; Lovelock, Kevin R.J.; Besley, Nicholas A.


Coby J. Clarke

Shusaku Hayama

Alexander Hawes

Jason P. Hallett

Thomas W. Chamberlain

Kevin R.J. Lovelock

Nicholas A. Besley


The Zn 1s valence-to-core (VtC) X-ray emission spectra of seven ionic liquids have been measured experimentally and simulated on the basis of time-dependent density-functional theory (TDDFT) calculations. Six of the ionic liquids were made by mixing [C8C1Im]X and Zn(II)X2 at three different ZnX2 mole fractions (0.33, 0.50, or 0.67) for X = Cl or Br, and a further ionic liquid was made by mixing [P6,6,6,14]Cl and a mole fraction of ZnCl2 of 0.33. Calculations were performed for the [ZnX4]2–, [Zn2X6]2–, and [Zn4X10]2– ions to capture the expected metal complex speciation. The VtC emission spectra showed three bands arising from single-electron processes that can be assigned to emission from ligand p-type orbitals, zinc d-orbitals, and ligand s-type orbitals. For all seven ionic liquids, the highest occupied molecular orbital arises from the ligand p orbitals, and the spectra for the different size metal complexes for the same X were found to be very similar, in terms of both relative peak intensities and peak energies. For both experiments and TDDFT calculations, there was an energy difference of 0.5 eV between the Cl-based and Br-based metal complexes for the ligand s and p orbitals, while the Zn 3d orbital energies were relatively unaffected by the identity of the ligand. The TDDFT calculations find that for the ions with symmetrically equivalent zinc atoms ([Zn2X6]2– and [Zn4X10]2–), the most appropriate core-ionized reference state has a core-hole that is localized on a single zinc atom. In this framework, the spectra for the larger ions can be viewed as a sum of spectra for the tetrahedral complex with a single zinc atom with small variations in the structure of the coordinating ligands. Because the spectra are relatively insensitive to small changes in the geometry of the ligands, this is consistent with the small variation in the spectra measured in the experiment.

Journal Article Type Article
Publication Date Nov 7, 2019
Journal Journal of Physical Chemistry A
Print ISSN 1089-5639
Electronic ISSN 1520-5215
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 123
Issue 44
Pages 9552-9559
APA6 Citation Clarke, C. J., Hayama, S., Hawes, A., Hallett, J. P., Chamberlain, T. W., Lovelock, K. R., & Besley, N. A. (2019). Zinc 1s Valence-to-Core X-ray Emission Spectroscopy of Halozincate Complexes. Journal of Physical Chemistry A, 123(44), 9552-9559.
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Additional Information This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review. To access the final edited and published work see


This file is under embargo until Oct 15, 2020 due to copyright restrictions.

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