Identification of hidden orbital contributions in the La0.65Sr0.35MnO3 valence band

Hybridization of electronic states and orbital symmetry in transition metal oxides are generally consideredkey ingredients in the description of both their electronic and magnetic properties. In the prototypical case ofLa0.65Sr0.35MnO3 (LSMO), a landmark system for spintronics applications, a description based solely on Mn 3dand O 2p electronic states is reductive.We thus analyzed elemental and orbital distributions in the LSMO valenceband through a comparison between density functional theory calculations and experimental photoelectronspectra in a photon energy range from soft to hard x rays. We reveal a number of hidden contributions, arisingspecifically from La 5p, Mn 4s, and O 2s orbitals, considered negligible in previous analyses; our resultsdemonstrate that all these contributions are significant for a correct description of the valence band of LSMOand of transition metal oxides in general.