Two classically identical expressions for the mutual information generally differ when the systems involved are quantum. This difference defines the quantum discord. It can be used as a measure of the quantumness of correlations. Separability of the density matrix describing a pair of systems does not guarantee vanishing of the discord, thus showing that absence of entanglement does not imply classicality. We relate this to the quantum superposition principle, and consider the vanishing of discord as a criterion for the preferred effectively classical states of a system, i.e., the pointer states.