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Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. We present a detailed joint experimental and theoretical investigation of the valence band electronic structure of single crystals of the model cuprate Ba 2 Cu 3 O 4 Cl 2 . This oxychloride system possesses a Cu 3 O 4 plane which can be regarded as a superposition of two subsystems: a Cu A O 2 cuprate plane and an extra Cu B site, and thus represents an ideal trial system for assessing the impact of deviations from the CuO 2 plane stoichiometry upon the electronic structure in cuprate materials. From polarization-dependent, k-resolved photoemission measurements the dispersion relations and symmetry of a number of the observed valence band features are determined and compared with the results of band structure calculations carried out within the LSDAϩU formalism, which include a detailed analysis of the character and symmetry of the individual bands. Upon electron removal, the extra copper site makes its presence felt via the formation of a second Zhang-Rice singlet located on the Cu B subsystem, in addition to that originating from the Cu A O 2 subsystem. The main valence band edge at ϳ2 eV binding energy is shown to be mainly due to bands involving combinations of O 2p x,y orbitals, some of which exhibit essentially pure O 2 p character. These low-lying oxygen bands are different in origin from the nonmixing O 2 p states observed, for example, at ( , ) in Sr 2 CuO 2 Cl 2 , as the orbital combination responsible for the latter is involved in Ba 2 Cu 3 O 4 Cl 2 in the formation of the Zhang-Rice singlet state on the Cu B sublattice. ͓S0163-1829͑98͒00717-6͔