Concentric Approximation for Fast and Accurate Numerical Evaluation of Nonadiabatic Coupling with Projector Augmented-Wave Pseudopotentials

We develop an efficient and accurate method for numerical evaluation of nonadiabatic (NA) coupling in the Kohn-Sham representation with projector augmented-wave (PAW) pseudopotentials that are commonly used in electronic structure calculations on nanoscale, condensed matter, and molecular systems. Without additional cost, the method provides an order of magnitude improvement in accuracy compared to the current technique, while it is 3-4 orders of magnitude faster than the exact evaluation. Atomic displacements over typical time steps in molecular dynamics (MD) simulations are much smaller than the size of the PAW core region, and therefore, evaluation of the NA in the core is simplified. The accuracy is demonstrated with three condensed matter systems. The method is robust to variation in the MD time step. The accurate NA coupling evaluation also helps in maintaining phase-consistency of the NA coupling and identifying trivial crossings of adiabatic states. The approach stimulates NAMD applications to modeling of modern materials and processes.

Automated summary

A highly efficient and accurate method for numerical evaluation of nonadiabatic coupling in the Kohn-Sham representation with PAW pseudopotentials has been developed. It provides a significant improvement in accuracy without additional cost, compared to the current technique, and is much faster. The method simplifies NA evaluation in the core region, is robust to variations in the MD time step, and helps to maintain phase consistency of coupling.