The electronic states of many Mott insulators, including iridates, are often conceptualized in terms of localized atomic states such as the famous $J_text{eff}=1/2$ state. Although, orbital hybridization can strongly modify such states and dramatically change the electronic properties of materials, probing this process is highly challenging. In this work, we directly detect and quantify the formation of dimer orbitals in an iridate material Ba$_5$AlIr$_2$O$_{11}$ using resonant inelastic x-ray scattering (RIXS). Sharp peaks corresponding to the excitations of dimer orbitals are observed and analyzed by a combination of density functional theory (DFT) calculations and theoretical simulations based on a Ir-Ir cluster model. Such partially delocalized dimer states lead to a re-definition of the angular momentum of the electrons and changes in the magnetic and electronic behaviors of the material. We use this to explain the reduction of the observed magnetic moment with respect to prediction based on atomic states. This study opens new directions to study dimerization in a large family of materials including solids, heterostructures, molecules and transient states.
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