X-ray absorption spectroscopy insights on the structure anisotropy and charge transfer in Chevrel Phase chalcogenides

Hyler, Forrest P.; Wuille Bille, Brian A.; Ortíz-Rodríguez, Jessica C.; Sanz-Matias, Ana; Roychoudhury, Subhayan; Perryman, Joseph T.; Patridge, Christopher J.; Singstock, Nicholas R.; Musgrave, Charles B.; Prendergast, David; Velázquez, Jesús M.

doi:10.1039/d1cp04851a

X-ray absorption spectroscopy insights on the structure anisotropy and charge transfer in Chevrel Phase chalcogenides

Journal Article · Fri Jul 01 00:00:00 EDT 2022 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d1cp04851a· OSTI ID:1887959

^[1]; ^[1]; ^[1]; ^[2]; Roychoudhury, Subhayan ^[2]; ^[3]; ^[4]; ^[5]; Musgrave, Charles B. ^[5]; ^[2]; ^[1]

University of California, Davis, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Stanford University, CA (United States)
D’Youville College, Buffalo, NY (United States)
University of Colorado, Boulder, CO (United States)

Here, the electronic structure and local coordination of binary (Mo₆T₈) and ternary Chevrel Phases (M_xMo₆T₈) are investigated for a range of metal intercalant and chalcogen compositions. We evaluate differences in the Mo L₃-edge and K-edge X-ray absorption near edge structure across the suite of chalcogenides M_xMo₆T₈ (M = Cu, Ni, x = 1–2, T = S, Se, Te), quantifying the effect of compositional and structural modification on electronic structure. Furthermore, we highlight the expansion, contraction, and anisotropy of Mo₆ clusters within these Chevrel Phase frameworks through extended X-ray absorption fine structure analysis. Our results show that metal-to-cluster charge transfer upon intercalation is dominated by the chalcogen acceptors, evidenced by significant changes in their respective X-ray absorption spectra in comparison to relatively unaffected Mo cations. These results explain the effects of metal intercalation on the electronic and local structure of Chevrel Phases across various chalcogen compositions, and aid in rationalizing electron distribution within the structure.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: National Science Foundation (NSF); Research Corporation for Science Advancement; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES); University of California, Davis

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515; AC02-98CH10886

OSTI ID:: 1887959

Alternate ID(s):: OSTI ID: 1875625

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 28 Vol. 24; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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