Magnetism in stoichiometric and off-stoichiometric MnO clusters: Insights from {it ab initio} theory

We study the composition dependent evolution of geometric and magnetic structures of MnO clusters within density functional theory. A systematic and extensive search through the potential energy surface is performed to identify the correct ground state, and significant isomers. We find that the magnetic structures in these MnO clusters are complex, which has been explained using the intrinsic electronic structure of the cluster, and analyzed using model Hamiltonian with parameters obtained from maximally localized Wannier functions. The calculated vertical displacement energies of off-stoichiometric MnO clusters compare well with the recent experimental results. Interestingly, the charged state of the cluster strongly influences the geometry and the magnetic structure of the cluster, which are very different from the corresponding neutral counterpart. Further, the importance of electron correlation in describing simple Mn-dimer and MnO clusters has been discussed within Hubbard model and hybrid exchange-correlation functional.