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The electronic configurations of Fe, Co, Ni, and Cu adatoms on graphene andgraphite have been studied by x-ray magnetic circular dichroism and chargetransfer multiplet theory. A delicate interplay between long-range interactionsand local chemical bonding is found to influence the adatom equilibriumdistance and magnetic moment. The results for Fe and Co are consistent withpurely physisorbed species having, however, different 3$d$-shell occupancies ongraphene and graphite ($d^{n+1}$ and $d^n$, respectively). On the other hand,for the late 3$d$ metals Ni and Cu a trend towards chemisorption is found,which strongly quenches the magnetic moment on both substrates.

Single 3$d$ transition metal atoms on multi-layer graphene systems: electronic configurations, bonding mechanisms and role of the substrate