Relationships between atomic diffusion mechanisms and ensemble transport coefficients in crystalline polymorphs

Benjamin J. Morgan, Paul A. Madden

OAI: oai:purehost.bath.ac.uk:publications/83cb5246-561a-4bf5-88f8-d7a10d63a698 • DOI: https://doi.org/10.1103/PhysRevLett.112.145901

Ionic transport in conventional ionic solids is generally considered to proceed via independent diffusion events or “hops.” This assumption leads to well-known Arrhenius expressions for transport coefficients, and is equivalent to assuming diffusion is a Poisson process. Using molecular dynamics simulations of the low-temperature B1, B3, and B4 AgI polymorphs, we have compared rates of ion hopping with corresponding Poisson distributions to test the assumption of independent hopping in these common structure types. In all cases diffusion is a non-Poisson process, and hopping is strongly correlated in time. In B1 the diffusion coefficient can be approximated by an Arrhenius expression, though the physical significance of the parameters differs from that commonly assumed. In low temperature B3 and B4, diffusion is characterized by concerted motion of multiple ions in short closed loops. Diffusion coefficients cannot be expressed in a simple Arrhenius form dependent on single-ion free energies, and intrinsic diffusion must be considered a many-body process.