All‐electron LCAO calculations of the LiF crystal phonon spectrum: Influence of the basis set,the exchange‐correlation functional,and the supercell size

For the first time the convergence of the phonon frequencies and dispersion curves in terms of the supercell size is studied in ab initio frozen phonon calculations on LiF crystal. Helmann–Feynman forces over atomic displacements are found in all‐electron calculations with the localized atomic functions (LCAO) basis using CRYSTAL06 program. The Parlinski–Li–Kawazoe method and FROPHO program are used to calculate the dynamical matrix and phonon frequencies of the supercells. For fcc lattice, it is demonstrated that use of the full supercell space group (including the supercell inner translations) enables to reduce essentially the number of the displacements under consideration. For Hartree–Fock (HF), PBE and hybrid PBE0, B3LYP, and B3PW exchange‐correlation functionals the atomic basis set optimization is performed. The supercells up to 216 atoms (3 × 3 × 3 conventional unit cells) are considered. The phonon frequencies using the supercells of different size and shape are compared. For the commensurate with supercell k ‐points the best agreement of the theoretical results with the experimental data is found for B3PW exchange‐correlation functional calculations with the optimized basis set. The phonon frequencies at the most non‐commensurate k ‐points converged for the supercell consisting of 4 × 4 × 4 primitive cells and ensures the accuracy 1–2% in the thermodynamic properties calculated (the Helmholtz free energy, entropy, and heat capacity at the room temperature). © 2009 Wiley Periodicals, Inc. J Comput Chem 2009