From a spin-resolved photoemission study on Bi2Sr2CaCu2O8 + δ the superconductor, we show experimentally that the first ionization state is of nearly pure singlet character. This is true both above and below the superconducting transition and in the presence of doping and band formation. This provides direct support for the existence and stability of Zhang-Rice singlets in high-temperature superconductors, justifying the ansatz of single-band models. Moreover, we establish this technique as an important probe for a wide range of cuprates and strongly correlated materials.
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