An ab initio study of electron-hole pairs in a correlated van der Waals antiferromagnet: NiPS₃

The recently discovered two-dimensional (2D) van der Waals magnet NiPS₃ provides a new route to examine many-body quasiparticles under 2D confinement. Excitons are of particular interest due to their strong coupling to the magnetic ground state in this material. Here, by using a first principles-based approach, we find bright excitons between 1.4 eV to 1.7 eV, similar to the sharp coherent and band edge excitons experimentally observed. Our analysis shows that each exciton in NiPS₃ is composed of a combination of d-d and charge-transfer character, where the relative ratio of each pairing configuration changes with exciton energy. Finally, the wave function of the electrons and holes is revealed to be spatially separated, with electrons and holes residing on different magnetic sublattices. This suggests a microscopic origin of the observed strong magneto-exciton coupling.