Abstract

Polarized Ni 2p photoabsorption spectra were measured for a single crystal of planar (D 4h) Ni II complex with low-spin 3d 8 configuration, K 2Ni(CN) 4·H 2O, in comparison with powder spectra of CaNi(CN) 4 and BaNi(CN) 4. Remarkably strong satellite bands are found besides the lowest Ni 2p–3d * atomic lines. Two features in the satellite show different polarization dependencies, and are assigned to the metal-to-ligand charge transfer (MLCT) transitions to out-of-plane e g π * and in-plane b 2g π * ligand orbitals, respectively, in good agreement with ab initio molecular orbital predictions. The low-lying ligand π * orbital is essential in the metal 2p photoabsorption of 3d transition metal compounds with strong π backbonding.

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