Finite-size effects on the molecular dynamics simulation of fast-ion conductors: A case study of lithium garnet oxide Li7La3Zr2O12

Abstract A useful tool to study ionic conduction mechanisms in fast-ion conductors is the molecular dynamics (MD) simulation performed on finite simulation cells with periodic boundary conditions. While there have been many studies of the effect of cell size on the thermodynamics and kinetics of simple liquids, the finite-size effect in fast-ion conductors remains elusive. This work presents a case study to investigate the finite-size effect on the phase transition, self-diffusivity, ionic conductivity, Haven ratio, thermodynamic factor, and Fickian diffusivity using lithium garnet oxide Li 7 La 3 Zr 2 O 12 as a model material. It was found that cell sizes influence extracted thermodynamic and kinetic characteristics in different ways with magnitude ranging from weak to strong. For Li 7 La 3 Zr 2 O 12 , reliable properties can be obtained with a 3 × 3 × 3 (5184 atoms) cell.