Quantum Spin Singlet and Classical Néel-Ordered Ground States in MoX3 (X = I, Br) Spin-3/2 Dimerized Antiferromagnetic Chain Crystals

We report that MoX3 (X = I, Br) are rare van der Waals materials that exhibit signatures of both quantum spin chains with a spin singlet ground state and classical Neel order. Bulk single crystals grown by chemical vapor transport exhibit classical antiferromagnetic ground states with a transition temperature of ~40 K as revealed by susceptibility and specific heat measurements. Above 40 K, the susceptibilities show the large, broad peaks associated with a quantum spin-singlet ground state and large singlet-triplet gaps of 21 meV and 25 meV. Monte Carlo simulations, density matrix renormalization-group calculations for finite spin-3/2 chains, and density functional theory reproduce the experimental behavior, confirming the interplay between strong one-dimensional intrachain and weak three-dimensional interchain couplings. MoX3 offers a unique platform for exploring quantum magnetism and magnetic excitations at the atomic chain limit, as these materials combine a 1D van der Waals motif, spin chain behavior, and classical interchain order.