Abstract
Anisotropic double exchange (DE) interaction is considered for the valence-delocalized [Fe 2.5+ Fe 2.5+] clusters with strong isotropic Anderson-Hasegawa DE coupling. The combined effect of the spin–orbit interaction and electron transfer between the excited states of the mixed-valence Fe ions results in the inter-ion anisotropic DE coupling. The coefficients of anisotropic DE coupling are linearly proportional to the parameters t 0 and t μ of the electron transfer (ET) in the ground and excited cluster states. The anisotropic DE coupling results in the zero-field splitting (ZFS) specific for the valence-delocalized clusters. The ZFS of the delocalized states of the anisotropic DE origin is described by the new effective ZFS Hamiltonian H ZFS t , which is active between the cluster states of different localizations, whereas the standard ZFS Hamiltonian, H ZFS 0 , acts in the localized states. The contributions of the anisotropic DE origin to the cluster ZFS parameters are linearly proportional to the ET (DE) parameters t 0 and t μ . The anisotropic DE contribution to the cluster ZFS parameters of the ground delocalized state Φ - 0 ( S max = 9 / 2 ) is of the same order of magnitude as the single-ion ZFS contributions.
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