Bright and Dark Excitons in CrSBr: Local Ligand-Field Character and Band-Coherent Optical Selection Rules

Abstract

Magnetic van der Waals semiconductors such as CrSBr host an intricate exciton landscape whose physical interpretation has converged only recently. A many-body Feynman diagrammatic approach based on quasiparticle self-consistent GW with electron-hole ladder vertex corrections to the screened Coulomb interaction has established the electronic band gap, excitonic orbital character, real-space extent, binding energies, and bosonic-coupling signatures of the bright XA exciton near 1.34 eV and the higher XB manifold near 1.8 eV. These results agree well with ARPES and magneto-optical experiments and supersede the early Rydberg-like assignment of the excitons. What has remained unresolved is why these intense bright excitons coexist, within a few tens of meV, with companion states that are several orders of magnitude darker despite drawing from essentially the same single-particle transition manifold. Here we show that brightness is a band-coherent property of the excitonic eigenfunctions: bright and dark partners are sublattice-symmetric and sublattice-antisymmetric superpositions of the same ligand-field-like Bloch transitions across the two Cr atoms of the orthorhombic primitive cell. The commonly used Frenkel and Wannier-Mott labels describe what an exciton is made of, but brightness requires a symmetry-adapted interference rule between transition dipoles. Disentangling this bare excitonic structure is a prerequisite for interpreting the optical response of CrSBr once magnon, phonon, and photon couplings are included.