Exchange-driven dimerization, magnetism, and insulating state in diamond (111)

Strong electron-electron interaction in ultraflat edge states can be responsible for correlated phases of matter, such as magnetism, charge-density wave, or superconductivity. Here we consider the diamond (111) surface that, after Pandey reconstruction, presents zigzag carbon chains, generating a flat surface band. By performing full structural optimization with hybrid functionals and neglecting spin polarization, we find that a substantial dimerization (0.090Å/0.076Å bond disproportionation in the PBE0/HSE06) occurs on the chains; a structural effect absent in calculations with functionals based on the local density/generalized gradient approximation. This dimerization is the primary mechanism for the opening of an insulating gap in the absence of spin polarization. The single-particle direct gap is 1.7eV (1.0eV) in the PBE0 (HSE06), comparable with the experimental optical gap of 1.47eV, and on the larger (smaller) side of the estimated experimental single-particle gap window of 1.57-1.87 eV, after inclusion of excitonic effects. However, by including spin polarization in the calculation, we find that the exchange interaction stabilizes a different ground state, undimerized, with no net magnetization and ferrimagnetic along the Pandey π chains with magnetic moments as large as 0.2-0.3μB in the PBE0. The direct single-particle band gap in the equal spin channel is approximately 2.2eV (1.5eV) with the PBE0 (HSE06) functional. Our work is relevant for systems with flat bands in general and wherever the interplay between structural, electronic, and magnetic degrees of freedom is crucial, as in twisted bilayer graphene, IVB atoms on IVB(111) surfaces such as Pb/Si(111), or molecular crystals.