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The electronic structure and magnetic moments of free Mn$_2^+$ and Mn$_3^+$are characterized by $2p$ x-ray absorption and x-ray magnetic circulardichroism spectroscopy in a cryogenic ion trap that is coupled to a synchrotronradiation beamline. Our results show directly that localized magnetic momentsof 5 $\mu_B$ are created by $3d^5 (^6\mathrm{S})$ states at each ionic core,which are coupled in parallel to form molecular high-spin states via indirectexchange that is mediated in both cases by a delocalized valence electron in asingly-occupied $4s$ derived orbital with an unpaired spin. This leads to totalmagnetic moments of 11 $\mu_B$ for Mn$_2^+$ and 16 $\mu_B$ for Mn$_3^+$, withno contribution of orbital angular momentum.

Direct Observation of High-Spin States in Manganese Dimer and Trimer Cations by X-ray Magnetic Circular Dichroism Spectroscopy in an Ion Trap