Large entropy change derived from the orbitally assisted three-centered two-electron σ bond formation in a metallic Li0.33VS2

Abstract

We discuss herein the emergence of a large entropy change in metallic Li0.33VS2 derived from the orbitally assisted loose σ bond formation. Comprehensive structural studies based on synchrotron x-ray and neutron diffraction analyses clarify the fabrication of ribbon chains at 375 K, consisting of multiple three-centered two-electron σ bonds based on the viewpoint of local chemical bonding. Although the metallic conductivity persists down to the lowest temperature measured, exceptionally large entropy change as a metal, as much as ΔS = 6.6 J/mol K, appears at the transition. Emergence of a large entropy change in a metallic state expects us the possible novel functional materials, such as a heat-storage material with rapid thermal response.

arXiv comment6 pages, 4 figures, to be published in Phys. Rev. B: Rapid Communications

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• Zigzag chain order of LiVSe${}_2$ developing away from the vanadium trimer phase transition boundary
• Electronic Landscape of Group-5 Transition Metal Ditellurides $M$Te${}_2$ ($M$ = V, Nb, Ta): Multiple Crystal Phases with Local Bonds and Flat Bands
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• Metallic state in the vicinity of molecular orbital crystallization in the d${}^1$ thiospinel ZnTi${}_2$S${}_4$ prepared via a reductive ion-exchange reaction