Transition metals, characterized by their partially filled d-orbitals, provide the basis for many of the most relevant processes in chemistry, biology, and physics. Embedded as single atoms or in small clusters, they give rise to exceptional optical, chemical, and magnetic properties. So far, it has proven impossible to disentangle the complex network of excited quantum states, which greatly hinders predicting and controlling of material properties. We employed double-resonant four-wave mixing spectroscopy to quantitatively resolve the bright and perturbing dark quantum states of the neutral copper dimer.