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

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

doi:10.1039/d1cp04851a

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

Phys Chem Chem Phys. 2022 Jul 21;24(28):17289-17294. doi: 10.1039/d1cp04851a.

Affiliations

¹ Department of Chemistry, University of California, One Shields Avenue, Davis, California, 95616, USA. [email protected].
² Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California, 94720, USA. [email protected].
³ Joint Center for Energy Storage Research, Lawrence Berkeley National Laboratory, Berkeley, California, 94720, USA.
⁴ Department of Chemical Engineering, Stanford University, 443 Via Ortega, Stanford, California, 94305, USA.
⁵ Department of Chemistry, D'Youville College, 320 Porter Avenue, Buffalo, New York, 14201, USA.
⁶ Department of Chemical and Biological Engineering, University of Colorado Boulder, Boulder, Colorado 80303, USA.

PMID: 35815404
DOI: 10.1039/d1cp04851a

Abstract

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.