Electronic excitation energies are determined using the CAM-B3LYP Coulomb-attenuated functional [T. Yanai Chem. Phys. Lett. 393, 51 (2004)], together with a standard generalized gradient approximation (GGA) and hybrid functional. The degree of spatial overlap between the occupied and virtual orbitals involved in an excitation is measured using a quantity Lambda, and the extent to which excitation energy errors correlate with Lambda is quantified. For a set of 59 excitations of local, Rydberg, and intramolecular charge-transfer character in 18 theoretically challenging main-group molecules, CAM-B3LYP provides by far the best overall performance; no correlation is observed between excitation energy errors and Lambda, reflecting the good quality, balanced description of all three categories of excitation. By contrast, a clear correlation is observed for the GGA and, to a lesser extent, the hybrid functional, allowing a simple diagnostic test to be proposed for judging the reliability of a general excitation from these functionals-when Lambda falls below a prescribed threshold, excitations are likely to be in very significant error. The study highlights the ambiguous nature of the term "charge transfer," providing insight into the observation that while many charge-transfer excitations are poorly described by GGA and hybrid functionals, others are accurately reproduced. (C) 2008 American Institute of Physics.