Description:
<jats:title>Abstract</jats:title><jats:p>The electronic structure of the Au<jats:sub>2</jats:sub><jats:sup>+</jats:sup> cation is essential for understanding its catalytic activity. We present the optical spectrum of mass‐selected Au<jats:sub>2</jats:sub><jats:sup>+</jats:sup> measured via photodissociation spectroscopy. Two vibrationally resolved band systems are observed in the 290–450 nm range (at ca. 440 and ca. 325 nm), which both exhibit rather irregular structure indicative of strong vibronic and spin‐orbit coupling. The experimental spectra are compared to high‐level quantum‐chemical calculations at the CASSCF‐MRCI level including spin‐orbit coupling. The results demonstrate that the understanding of the electronic structure of this simple, seemingly H<jats:sub>2</jats:sub><jats:sup>+</jats:sup>‐like diatomic molecular ion strictly requires multireference and relativistic treatment including spin‐orbit effects. The calculations reveal that multiple electronic states contribute to each respective band system. It is shown that popular DFT methods completely fail to describe the complex vibronic pattern of this fundamental diatomic cation.</jats:p>