Density Functional Theory Half-Electron Self-Energy Correction for Fast and Accurate Nonadiabatic Molecular Dynamics.

TLDR: In this paper, density functional theory (DFT) half-electron self-energy correction can reproduce the bandgap, effective masses of carriers, luminescence line widths, NAC, and excited-state lifetimes of the two systems at the hybrid functional level while the computational cost remains at that of the Predew-Burke-Ernzerhof functional.

Abstract: The nonadiabatic (NA) process is crucial to photochemistry and photophysics and requires an atomistic understanding. However, conventional NA molecular dynamics (MD) for condensed-phase materials on the nanoscale are generally limited to the semilocal exchange-correlation functional, which suffers from the bandgap and thus NA coupling (NAC) problems. We consider TiO2 and a black phosphorus monolayer as two prototypical systems, perform NA-MD simulations of nonradiative electron-hole recombination, and demonstrate for the first time that density functional theory (DFT) half-electron self-energy correction can reproduce the bandgap, effective masses of carriers, luminescence line widths, NAC, and excited-state lifetimes of the two systems at the hybrid functional level while the computational cost remains at that of the Predew-Burke-Ernzerhof functional. Our study indicates that the DFT-1/2 method can greatly accelerate NA-MD simulations while maintaining the accuracy of the hybrid functional, providing an advantage for studying photoexcitation dynamics for large-scale condensed-phase materials.