Ab initio up to the melting point: anharmonicity and vacancies in aluminium
B. Grabowski, L. Ismer, T. Hickel, J. Neugebauer.
Physical Review B, 79, 134106, 1-16, (2009)
We propose a fully ab initio based integrated approach to determine the volume and temperature dependent free-energy surface of nonmagnetic crystalline solids up to the melting point. The approach is based on density-functional theory calculations with a controlled numerical accuracy of better than 1 meV/atom. It accounts for all relevant excitation mechanisms entering the free energy including electronic, quasiharmonic, anharmonic, and structural excitations such as vacancies. To achieve the desired accuracy of <1 meV/atom for the anharmonic free-energy contribution without losing the ability to perform these calculations on standard present-day computer platforms, we develop a numerically highly efficient technique: we propose a hierarchical scheme - called upsampled thermodynamic integration using Langevin dynamics - which allows for a significant reduction in the number of computationally expensive ab initio configurations compared to a standard molecular dynamics scheme. As for the vacancy contribution, concentration-dependent pressure effects had to be included to achieve the desired accuracy. Applying the integrated approach gives us direct access to the free-energy surface F(V,T) for aluminum and derived quantities such as the thermal expansion coefficient or the isobaric heat capacity and allows a direct comparison with experiment. A detailed analysis enables us to tackle the long-standing debate over which excitation mechanism (anharmonicity vs vacancies) is dominant close to the melting point.