The electronic structures of a wide range of transition-metal compounds, including Cu, Ni, Co, Fe, and Mn oxides and sulfides, with metal valences ranging from 2+ to 4+, have been investigated by a cluster-type configuration-interaction analysis of the core-level 2p x-ray photoemission spectra. We show that by including the d-d exchange interaction (retaining only diagonal terms) and an anisotropic metal-ligand hybridization in the model, these spectra can be well reproduced, and so can be used to deduce quantitatively values for the ligand-to-metal charge-transfer energy Δ, the on-site d-d Coulomb repulsion energy U, and the metal-ligand transfer integrals T. Systematics for Δ and U are generally consistent with those found from previous valence-band studies and follow expected chemical trends. By using values of Δ and U found from this model, we show that most of the transition-metal compounds studied in this work can be classified in the charge-transfer regime of the Zaanen-Sawatzky-Allen diagram. A few exceptions to these systematics have been found. Small U values found for pyrite-type

{CoS}_{2}

and

{FeS}_{2}

and large T values for Mn perovskite oxides, as well as the neglect of other mechanisms such as exciton satellites, may indicate a limitation of the local-cluster model.

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