Paper detail

A fully quantum mechanical calculation of the diffusivity of hydrogen in iron using the tight binding approximation and path integral theory

We present calculations of free energy barriers and diffusivities as functions of temperature for the diffusion of hydrogen in bcc-Fe. This is a fully quantum mechanical approach since the total energy landscape is computed using a new self consistent, transferable tight binding model for interstitial impurities in magnetic iron. Also the hydrogen nucleus is treated quantum mechanically and we compare here two approaches in the literature both based in the Feynman path integral formulation of statistical mechanics. We find that the quantum transition state theory which admits greater freedom for the proton to explore phase space gives result in better agreement with experiment than the alternative which is based on fixed centroid calculations of the free energy barrier. We also find results in better agreement compared to recent centroid molecular dynamics (CMD) calculations of the diffusivity which employed a classical interatomic potential rather than our quantum mechanical tight binding theory. In particular we find first that quantum effects persist to higher temperatures than previously thought, and conversely that the low temperature diffusivity is smaller than predicted in CMD calculations and larger than predicted by classical transition state theory. This will have impact on future modeling and simulation of hydrogen trapping and diffusion.