Orbital-selective hybridization shapes the electronic structure of layered antiferromagnetic CrPS4

Layered antiferromagnetic semiconductors combine electronic correlations with pronounced metal-ligand hybridization, but how these competing interactions hierarchically shape their electronic structure remains largely unexplored. Here, we resolve the orbital-selective electronic structure of the van der Waals antiferromagnet chromium thiophosphate (CrPS 4 ) using angle-resolved photoemission spectroscopy above and below its Néel temperature, complemented by density functional theory (DFT)+ U calculations. We identify a clear orbital separation within the Cr 3 d states: weakly hybridized, spin-polarized t 2g states that stabilize robust local magnetism and strongly hybridized e g -ligand states forming bonding-antibonding pairs that govern covalency and optical activity. Systematic variation of U shows that the t 2g -derived states are markedly correlation sensitive, whereas the nominally unoccupied e g -ligand manifold, populated partially via hybridization, remains comparatively U insensitive. This orbital-selective response unveils distinct control parameters within a single d shell and suggests promising pathways to tune magnetic and optical functionalities independently via external control of correlation strength and metal-ligand coupling.