Considering simple model problems, symmetric mixed-valence compounds an studied by both accurate ab initio configuration interaction (CI) and standard (B3LYP) density functional theory (DFT) calculations. The DFT estimates of the effective hopping integral t for mixed-valence compounds are generally smaller (by 20%) than the CI values, in contrast to those of the exchange coupling constant in magnetic systems which are usually overestimated. Qualitatively divergent behaviors of DFT versus CI results have been found in some cases. Possible origins of these discrepancies are discussed. (C) 3000 Elsevier Science B.V. All rights reserved.