Efficient Modeling of Quantum Dynamics of Charge Carriers in Materials Using Short Nonequilibrium Molecular Dynamics

The Journal of Physical Chemistry Letters. 2023. Vol. 14. No. 37. P. 8289–8295.

Wang B., Wu Y., Liu D., Vasenko A., Casanova D., Prezhdo O. V.

Nonadiabatic molecular dynamics provides essential insights into excited-state processes, but it is computationally intense and simplifications are needed. The classical path approximation provides critical savings. Still, long heating and equilibration steps are required. We demonstrate that practical results can be obtained with short, partially equilibrated ab initio trajectories. Once the system’s structure is adequate and essential fluctuations are sampled, the nonadiabatic Hamiltonian can be constructed. Local structures require only 1−2 ps trajectories, as demonstrated with point defects in metal halide perovskites. Short trajectories represent anharmonic motions common in defective structures, an essential improvement over the harmonic approximation around the optimized geometry. Glassy systems, such as grain boundaries, require different simulation protocols, e.g., involving machine learning force fields. 10-fold shorter trajectories generate 10−20% time scale errors, which are acceptable, given experimental uncertainties and other approximations. The practical NAMD protocol enables fast screening of excited-state dynamics for rapid exploration of new materials.

Keywords: DFT, quantum dynamics, metal halide perovskites, Charge carriers mobility, Nonequilibrium Molecular Dynamics

Publication based on the results of: Quantum phenomena in solid-state composite systems (2023)