Failure of DFT-based computations for a stepped-substrate-supported correlated Co wire

Density functional theory (DFT) has been immensely successful in its ability to predict physical properties and, in particular, structures of condensed matter systems. Here, however, we show that DFT qualitatively fails to predict the dimerized structural phase for a monatomic Co wire that is self-assembled on a vicinal (i.e. stepped) Cu(111) substrate. To elucidate the nature of this failure, we compute the energetics of a Co chain on a Cu surface, step, and notch and embedded in bulk. The results demonstrate that increasing Co coordination extinguishes the dimerization, indicating that the failure of DFT for Co on the Cu step arises from excessive hybridization, which both weakens the ferromagnetic correlations that drive the dimerization and increases the bonding that opposes dimerization. Additionally, we show that including local interactions via DFT + U or DFT + dynamical mean field theory (DMFT) does not restore the dimerization for the stepped-substrate-supported wire, although the Co wire does dimerize in DFT + DMFT for the isolated vacuum case. This system can serve as a benchmark for future electronic structure methods.