Maximum Spin Polarization in Chromium Dimer Cations as Demonstrated by X-ray Magnetic Circular Dichroism Spectroscopy

X-ray magnetic circular dichroism spectroscopy has been used to characterize the electronic structure and magnetic moment of Cr₂⁺. Our results indicate that the removal of a single electron from the 4sσ_g bonding orbital of Cr₂ drastically changes the preferred coupling of the 3d electronic spins. While the neutral molecule has a zero-spin ground state with a very short bond length, the molecular cation exhibits a ferromagnetically coupled ground state with the highest possible spin of S=11/2, and almost twice the bond length of the neutral molecule. This spin configuration can be interpreted as a result of indirect exchange coupling between the 3d electrons of the two atoms that is mediated by the single 4s electron through a strong intraatomic 3d-4s exchange interaction. Our finding allows an estimate of the relative energies of two states that are often discussed as ground-state candidates, the ferromagnetically coupled ¹²Σ and the low-spin ²Σ state. The removal of a single electron from the 4sσ_g bonding orbital of Cr₂ fully localizes all the 3d electrons and drastically changes the preferred coupling of their spins. The molecular cation exhibits a ferromagnetically coupled ground state with the highest possible spin of S=11/2, and almost twice the bond length of the neutral molecule. This spin configuration can be interpreted as a result of indirect exchange coupling.