The influence of high-energy local orbitals and electron-phonon interactions on the band gaps and optical spectra of hexagonal boron nitride

We report theoretical results of hexagonal boron nitride (h-BN) using state-of-the-art first principles methods, focusing on providing well-converged quasiparticle band structures, and upon this unraveling the intricate interplay between the quasiparticle excitations, electron-phonon interactions (EPIs), and excitonic effects. Including high-energy local orbitals (HLOs) is crucial in all-electron linearized augmented plane waves (LAPWs) -based GW calculations, which widens the quasiparticle direct (indirect) band gaps by 0.22 (0.23) eV, and opens the GW0 direct (indirect) band gaps to 6.81 (6.25) eV. EPIs, on the other hand, reduce them to 6.62 (6.03) eV at 0 K and 6.60 (5.98) eV at 300 K. With clamped structure, the first absorption peak is at 6.07 eV, originating from the direct exciton at H in the Brillouin zone (BZ). After including lattice vibrations using the dynamical Heine-Allen-Cardona method, this peak shifts to 5.83 eV at 300 K, lower than the experimental value of ~6.00 eV. This accuracy is acceptable to an ab initio description of excited states with no adjustable parameter, and including HLOs plays a determinant role. The shoulder at the lower energy side of the first absorption peak is still absent, which we believe is related to the indirect excitons. This effect is absent in the present treatment, therefore we call for further improved method in future studies.