Spectroscopic disentanglement of the quantum states of highly excited Cu₂

Transition metals, characterised 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 prediction and control of material properties. Here, we apply two-colour resonant four-wave mixing to quantitatively resolve the quantum states of the neutral copper dimer. This allows us to unwind the individual spectral lines by isotopic composition and rotational quantum number and reveals a rich network of bright and perturbing dark states. While this work presents a road map for the experimental study of the bonding between and with transition metal atoms, it also provides experimental reference data for prospective quantum chemical approaches on handling systems with a high density of states.