Microscopic evidence for a Zhang-Rice triplet state in the van der Waals antiferromagnet, NiPS$_3$

Abstract

Quantum-entangled states underpin many emergent phenomena in quantum materials, yet their direct experimental identification remains a challenge. NiPS$_3$, a van der Waals antiferromagnet exhibiting a resolution-limited magnetic exciton in its ordered phase, has been proposed to host a many-body entangled Zhang-Rice triplet state. Here, using $^{33}$S nuclear magnetic resonance (NMR) on $^{33}$S-enriched NiPS$_3$ single crystals, we provide microscopic evidence for this charge-transfer state. The $^{33}$S and $^{31}$P Knight shifts as a function of temperature reveal a unified spin-triplet configuration arising from strong hybridization between a self-doped hole in the S $3p$ orbitals and a hole in Ni $3d$ orbitals. Furthermore, the $^{33}$S nuclear spin-lattice relaxation rate exhibits a power-law divergence as it approaches the Néel temperature $T_N=155$ K, indicating critical slowing down of collective charge fluctuations consistent with spin-nematic correlations. These results reveal a spin-charge-intertwined ground state and establish the microscopic foundation for the exceptional coherence of the magnetic exciton in NiPS$_3$.