An investigation of the electronic structure of Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} (0{<=}x{<=}3) thiospinel spin-crossover materials by X-ray absorption spectroscopy and electronic structure calculations

Hayes, John R.

doi:10.1016/J.JSSC.2012.08.057

Title: An investigation of the electronic structure of Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} (0{<=}x{<=}3) thiospinel spin-crossover materials by X-ray absorption spectroscopy and electronic structure calculations

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Abstract

The spin-crossover (SCO) transition is an interesting phenomenon in which a metal center transitions from a low-spin state to a high-spin state (or vice versa) upon some external perturbation. Only a few studies have investigated the SCO transition in crystalline compounds and the Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} thiospinels present an opportunity for such a study. Fe K-XANES has been used to investigate the changes in the electronic structure of these materials as Ti is substituted for Sn. The room-temperature Fe K-edge XANES spectra showed that the pre-edge intensity increased with increasing Ti content as a result of the Fe-S bond becoming more covalent. Ti K- and S K-edge XANES spectra confirmed this analysis. Electronic structure calculations were also performed to aid in the interpretation of the XANES spectra. Temperature-dependent Fe K-edge XANES spectra were further collected to study the SCO transition and showed that the main-edge features decreased in intensity with decreasing temperature, corresponding to variations in the average Fe{sup 2+} spin-state. - Graphical abstract: The Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} spin-crossover materials have been investigated by XANES. The pre-edge region of the Fe K-edge spectra increases with greater Ti incorporation because of the Fe-S bonds becoming more covalent.more »« less

Authors:

Hayes, John R. ^[1]

Department of Chemistry, University of Saskatchewan, Saskatoon, SK, Canada S7N 5C9 (Canada)

Publication Date:: Tue Jan 15 00:00:00 EST 2013

OSTI Identifier:: 22131222

Resource Type:: Journal Article

Journal Name:: Journal of Solid State Chemistry

Additional Journal Information:: Journal Volume: 197; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; ABSORPTION SPECTROSCOPY; ELECTRONIC STRUCTURE; HIGH SPIN STATES; INTERACTIONS; SPECTRA; SPIN; TEMPERATURE DEPENDENCE; X-RAY SPECTROSCOPY

Citation Formats


                    Hayes, John R., and Grosvenor, Andrew P., E-mail: andrew.grosvenor@usask.ca. An investigation of the electronic structure of Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} (0{<=}x{<=}3) thiospinel spin-crossover materials by X-ray absorption spectroscopy and electronic structure calculations.  United States: N. p., 2013. 
        Web.  doi:10.1016/J.JSSC.2012.08.057.

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                    Hayes, John R., & Grosvenor, Andrew P., E-mail: andrew.grosvenor@usask.ca. An investigation of the electronic structure of Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} (0{<=}x{<=}3) thiospinel spin-crossover materials by X-ray absorption spectroscopy and electronic structure calculations.  United States.  https://doi.org/10.1016/J.JSSC.2012.08.057

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                    Hayes, John R., and Grosvenor, Andrew P., E-mail: andrew.grosvenor@usask.ca. 2013.  
        "An investigation of the electronic structure of Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} (0{<=}x{<=}3) thiospinel spin-crossover materials by X-ray absorption spectroscopy and electronic structure calculations".  United States.  https://doi.org/10.1016/J.JSSC.2012.08.057.

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@article{osti_22131222,

  title        = {An investigation of the electronic structure of Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} (0{<=}x{<=}3) thiospinel spin-crossover materials by X-ray absorption spectroscopy and electronic structure calculations},

  author       = {Hayes, John R. and Grosvenor, Andrew P., E-mail: andrew.grosvenor@usask.ca},

  abstractNote = {The spin-crossover (SCO) transition is an interesting phenomenon in which a metal center transitions from a low-spin state to a high-spin state (or vice versa) upon some external perturbation. Only a few studies have investigated the SCO transition in crystalline compounds and the Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} thiospinels present an opportunity for such a study. Fe K-XANES has been used to investigate the changes in the electronic structure of these materials as Ti is substituted for Sn. The room-temperature Fe K-edge XANES spectra showed that the pre-edge intensity increased with increasing Ti content as a result of the Fe-S bond becoming more covalent. Ti K- and S K-edge XANES spectra confirmed this analysis. Electronic structure calculations were also performed to aid in the interpretation of the XANES spectra. Temperature-dependent Fe K-edge XANES spectra were further collected to study the SCO transition and showed that the main-edge features decreased in intensity with decreasing temperature, corresponding to variations in the average Fe{sup 2+} spin-state. - Graphical abstract: The Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} spin-crossover materials have been investigated by XANES. The pre-edge region of the Fe K-edge spectra increases with greater Ti incorporation because of the Fe-S bonds becoming more covalent. Highlights: Black-Right-Pointing-Pointer Cu{sub 2}FeSn{sub 3-x}Ti{sub x}S{sub 8} thiospinels were investigated by XANES. Black-Right-Pointing-Pointer The covalency of the Fe-S and Ti-S bonds increases with greater Ti incorporation. Black-Right-Pointing-Pointer T-dependent Fe K-edge XANES spectra were collected to investigate SCO transitions. Black-Right-Pointing-Pointer Covalent bonding makes study of the SCO transition difficult by Fe K-edge XANES. Black-Right-Pointing-Pointer The bonding interactions were investigated through examination of S K-edge spectra.},

  doi          = {10.1016/J.JSSC.2012.08.057},

  url          = {https://www.osti.gov/biblio/22131222},
  journal      = {Journal of Solid State Chemistry},

  issn         = {0022-4596},

  number       = ,

  volume       = 197,

  place        = {United States},

  year         = {Tue Jan 15 00:00:00 EST 2013},

  month        = {Tue Jan 15 00:00:00 EST 2013}

}

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