Fermi-Level Metal-d Character of Group-6 Bis-Hexahapto Bilayer Graphene

Abstract

Superconductivity in graphite intercalation compounds requires occupancy of a carbon-derived interlayer band filled by charge from an electropositive intercalant. Bis-hexahapto (eta6-eta6) coordination binds transition metals covalently to two graphene sheets with little charge transfer -- the mechanism that defines this chemistry removes the donation on which intercalated-graphite superconductivity rests. We ask, for group-6 Cr, Mo and W in bilayer graphene, whether Fermi-level states retain the interstitial, carbon-p character of ionic references, with bulk CaC6 and same-cell C12Ca/C12Li controls. Electron-phonon coupling is not computed. At one metal per gallery (C12M), the ionic controls retain 68 and 45 per cent, respectively, of gallery spectral weight in atom-masked interstitial regions at EF; the group-6 systems retain 15, 22 and 23 per cent. The contrast is compositional: group-6 galleries carry more absolute interstitial weight than C12Li, but projected density of states within +/-0.15 eV of EF is carbon p dominated in the ionic references and metal d dominated (~73 per cent) in all three group-6 bilayers. Every system studied is metallic; they differ in what carries the Fermi surface. Geometrically, eta6-eta6 coordination requires AA stacking and reverses the intrinsic Bernal preference by 400-600 meV wherever metal is present. Ordered phases are metastable against bulk metal (+2.9-5.0 eV per atom) but bound against isolated atoms (-1.6-4.1 eV); instability ordering (Cr least, W most) matches Cr > Mo > W reactivity. C12Cr is metallic; tungsten alone carries 0.65 muB. Bis-hexahapto intercalation delivers strong interlayer bonding and a definite AA registry, but not the interlayer-band character associated with superconducting graphite intercalation compounds.