In this work, we performed a detailed analysis of the x-ray photoemission spectroscopy (XPS) of the Mn 2ppeak for Mn3O4(001) thin films. This is a challenging task since Mn3O4is composed of two different cations, Mn2+at tetrahedral and Mn3+at octahedral sites, which both contribute to the XPS spectra. The oxide spectra consist of many multiplets arising from the angular momentum coupling of the open Mn 2pand 3dshells, thus increasing the spectrums' complexity. Moreover, the energy spacing and intensities of the different multiplets also reflect the covalent mixing between Mn 3dand O 2pshells. However, we show that a detailed analysis, which provides relevant information about the cations in the oxide structure, is possible. We prepared experimentally different Mn3O4films on Au(111), and their structure was monitored with the diffraction pattern obtained with low-energy electron diffraction. The Mn 2pspectra were fit, guided by cluster model theoretical predictions, and checked for films prepared at different oxygen partial pressures. Therefore, we could observe the Mn2+and Mn3+cations' relative concentration in the Mn 2pmains peaks.
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