Exciton dispersion and exciton-phonon interaction in solids by time-dependent density functional theory

Understanding, predicting, and ultimately controlling exciton band structure and exciton dynamics are central to diverse chemical and materials problems. Here, we have developed a first-principles method to determine exciton dispersion and exciton-phonon interaction in semiconducting and insulating solids based on time-dependent density functional theory. The first-principles method is formulated in planewave bases and pseudopotentials and can be used to compute exciton band structures, exciton charge density, ionic forces, the non-adiabatic coupling matrix between excitonic states, and the exciton-phonon coupling matrix. Based on the spinor formulation, the method enables self-consistent noncollinear calculations to capture spin-orbital coupling. Hybrid exchange-correlation functionals are incorporated to deal with long-range electron-hole interactions in solids. A sub-Hilbert space approximation is introduced to reduce the computational cost without loss of accuracy. For validations, we have applied the method to compute the exciton band structure and exciton-phonon coupling strength in transition metal dichalcogenide monolayers; both agree very well with the previous GW-Bethe-Salpeter equation and experimental results. This development paves the way for accurate determinations of exciton dynamics in a wide range of solid-state materials.

Automated summary

In this study, a first-principles method based on time-dependent density functional theory is developed to determine exciton dispersion and exciton-phonon interaction in semiconducting and insulating solids. The method can compute exciton band structures, exciton charge density, ionic forces, the non-adiabatic coupling matrix between excitonic states, and the exciton-phonon coupling matrix. Validations show good agreement with previous GW-Bethe-Salpeter equation and experimental results. This development enables accurate determinations of exciton dynamics in a wide range of solid-state materials.