Local multiplet formation around a single vacancy in graphene: an effective Anderson model analysis based on the block-Lanczos DMRG method

Abstract

To better understand the electronic structure of a single vacancy in graphene, we study the ground state property of an effective Anderson model, consisting of three dangling $sp^2$ orbitals of the surrounding carbon atoms around the vacancy and the $π$ orbitals of carbon atoms that form the honeycomb lattice with a single vacancy. Employing the block-Lanczos density-matrix renormalization group method, we show that there are two phases in the relevant parameter space, i.e., a nonmagnetic phase in the weak coupling region and a free magnetic moment phase in the realistic parameter region. The systematic analysis finds that, in the free magnetic moment phase, local multiplets of the doubly degenerate irreducible representation of the $\mathcal{C}_3$ point group with spin 1 become dominant in the ground state, and approximately half of this local spin 1 is screened by electrons in the surrounding $π$ orbitals, indicating the emergence of the residual spin-1/2 free magnetic moment. Furthermore, we find that the emergence of the free magnetic moment is robust against carrier doping, which is in sharp contrast to the case of graphene with an adatom, thus explaining the qualitative difference observed experimentally in these two classes of systems. We also find the enhancement of the spin correlation function between $π$ electrons around the vacancy and those in the conduction band away from the vacancy in the undoped case, as compared to that in the doped case, while the spin correlation function between the $σ$ electrons in the $sp^2$ dangling orbitals around the vacancy and the $π$ electrons in the conduction band remains large in both undoped and doped cases. Our calculations thus support qualitatively the previous experiment that suggests the emergence of free magnetic moment with two distinct origins.