Insight into interrelation between single-particle and collective diffusion in binary melts

Abstract

The interrelation between the kinetics of single-particle (tracer) and collective diffusion in a binary melt is investigated theoretically within the framework of the Mori–Zwanzig formalism of statistical mechanics. An analytical expression for the Onsager coefficient for mass transport and two self-diffusion coefficients of species in a binary melt is derived using analysis based on the generalized Langevin equation. The derived expression naturally accounts for manifestation of microscopic (dynamic) cross-correlation effects in the kinetics of collective diffusion. Hence, it presents an explicit extension of the well-known Darken equation which is currently often used for expressing collective interdiffusion in terms of the two self-diffusion coefficients. An application of our analysis for interpretation of recent experimental data on the interrelation between the kinetics of single-particle and collective diffusion in Al-rich Ni–Al melts is demonstrated.