The temperature-dependent diffusion coefficients of interstitial hydrogen, deuterium, and tritium in nickel are computed using transition state theory. The coefficient of thermal expansion, the enthalpy and entropy of activation, and the pre-exponential factor of the diffusion coefficient are obtained from ab initio total energy and phonon calculations including the vibrations of all atoms. Numerical results reveal that diffusion between octahedral interstitial sites occurs along an indirect path via the metastable tetrahedral site and that both the migration enthalpy and entropy are strongly temperature dependent. However, the migration enthalpy and entropy are coupled so that the diffusion coefficient is well described by a constant activation energy, i.e., D = D 0 exp͓−Q / ͑RT͔͒, with Q = 45.72, 44.09, and 43.04 kJ/ mol and D 0 = 3.84ϫ 10 −6 , 2.40ϫ 10 −6 , 1.77 ϫ 10 −6 m 2 s −1 for H, D, and T, respectively. The diffusion of deuterium and tritium is computed to be slower than that of hydrogen only at temperatures above 400 K. At lower temperatures, the order is reversed in excellent agreement with experiment. The present approach is applicable to atoms of any mass as it includes the full coupling between the vibrational modes of the diffusing atom with the host lattice.

The temperature-dependent mass diffusion coefficient is computed using transition state theory. Ab initio supercell phonon calculations of the entire system provide the attempt frequency, the activation enthalpy, and the activation entropy as a function of temperature. Effects due to thermal lattice expansion are included and found to be significant. Numerical results for the case of hydrogen in nickel demonstrate a strong temperature dependence of the migration enthalpy and entropy. Trapping in local minima along the diffusion path has a pronounced effect especially at low temperatures. The computed diffusion coefficients with and without trapping bracket the available experimental values over the entire temperature range between 0 and 1400 K.

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