Long-term atomistic finite-temperature substitutional diffusion

Simulating long-term mass diffusion kinetics with atomic precision is important to predict chemical and mechanical properties of alloys over time scales of engineering interest in applications, including (but not limited to) alloy heat treatment, corrosion resistance, and hydrogen embrittlement. We present a new strategy to bridge from the time scale of atomic vibrations to that of vacancy-mediated atomic hops by a combination of statistical mechanics-based Gaussian phase packets (GPP) relaxation and a nudged elastic band (NEB)-facilitated harmonic transition state theory (H-TST) time update. We validate the approach by simulating bulk self-diffusion in copper, segregation of vacancies and magnesium to a stacking fault and a symmetric tilt grain boundary in aluminum, and the interdiffusion of copper in α -brass, modeled with embedded atom method (EAM) potentials. The method correctly predicts the kinetics in bulk copper and equilibrium impurity concentrations in aluminum, in agreement with the Langmuir-McLean solution in the dilute limit. Moreover, our reduced-order model for non-dilute alloys correctly captures the movement on an inert marker placed at the interface of an asymmetric interdiffusion couple, as validated by the comparison of marker displacements with Kirkendall experiments. Notably, this technique can reach realistic diffusion time scales of days, weeks, and even years in a computational time of hours, demonstrating its capability to study the long-term chemo-thermo-mechanically coupled behavior of atomic ensembles.