Convergence of Time-Derivative Nonadiabatic Couplings in Plane-Wave DFT Calculations.

Accurate prediction of charge carrier relaxation rates is essential to design molecules and materials with the desired photochemical properties for applications like photocatalysis and solar energy conversion. Nonadiabatic molecular dynamics allows one to simulate the relaxation process of excited charge carriers. Plane-wave density functional theory (DFT) calculations make the time-derivative nonadiabatic couplings (TNACs) simple to compute because the basis is independent of the atomic positions. However, the effect of the kinetic energy cutoff for the plane-wave basis on the accuracy of the dynamics has not been studied. Here, we examine the effect of the kinetic energy cutoff on the TNACs and decay time scales for the prototypical model system of tetracene. These calculations show that the choice of kinetic energy cutoff can change the relaxation time by up to 30%. The relaxation times of states that have small TNACs to other states or are far from degenerate are more sensitive to the kinetic energy cutoff than those of states with large TNACs or near degeneracies. A kinetic energy cutoff of 60 Ry is sufficient for all states to reach semiquantitative agreement (absolute error <10%) with the decay times of our 110 Ry reference data, and a cutoff of 80 Ry is required for all states to reach quantitative agreement (absolute error <2%).