Ab initio study of the structural, elastic, vibrational and thermodynamic properties of the hexagonal boron nitride: Performance of LDA and GGA

Abstract

A first principles quantum mechanical approach is used to investigate the structural, elastic, vibrational and thermodynamic properties of the hexagonal boron nitride ( h-BN) in the framework of the pseudopotential plane wave density-functional perturbation theory for the two popular exchange-correlation functionals: local density approximation and the revised Perdew–Burke–Ernzerhof generalized gradient approximation [Y. Zhang, W. Yang, Phys. Rev. Lett, 80 (1998), 890]. The LDA calculations of the structural parameters are in good agreement with experimental results, whereas GGA largely overestimated them. The computed elastic constants are improved by performing the calculations at room temperature and using the experimental lattice parameters. A good agreement with the experimental data is obtained for the phonon frequencies using both functionals. The thermodynamic properties such as the thermal equation of state, the in-plane and out-of-plane thermal expansion coefficients (LTEC), the bulk modulus and the heat capacity are calculated at the experimental lattice parameters using the quasiharmonic approximation (+ an empirical anharmonic term) for the Helmholtz free energy. Anharmonic corrections are important at high temperature. A good agreement with the experimental data for the LTEC has been obtained with the GGA functional, especially for the out-of-plane LTEC. In contrast with recent experimental findings, our calculated bulk modulus decreases with temperature for both functionals. This (decreasing) behavior is in a good agreement with other experimental data. The constant pressure heat capacity calculated with LDA and GGA is in very good agreement with experimental results.