Abstract
Using density-functional perturbation theory and the Grüneisen formalism, we directly calculate the linear thermal expansion coefficients (TECs) of a hexagonal bulk system in the crystallographic and directions. The TEC calculation depends critically on the evaluation of a temperature-dependent quantity , which is the integral of the product of heat capacity and , of frequency and strain type , where is the phonon density of states weighted by the Grüneisen parameters. We show that to determine the linear TECs we may use minimally two uniaxial strains in the direction and either the or direction. However, a uniaxial strain in either the or direction drastically reduces the symmetry of the crystal from a hexagonal one to a base-centered orthorhombic one. We propose to use an efficient and accurate symmetry-preserving biaxial strain in the plane to derive the same result for . We highlight that the Grüneisen parameter associated with a biaxial strain may not be the same as the average of Grüneisen parameters associated with two separate uniaxial strains in the and directions due to possible preservation of degeneracies of the phonon modes under a biaxial deformation. Large anisotropy of TECs is observed where the linear TEC in the direction is about 1.8 times larger than that in the or direction at high temperatures. Our theoretical TEC results are compared with experiment. The symmetry-preserving approach adopted here may be applied to a broad class of two lattice-parameter systems such as hexagonal, trigonal, and tetragonal systems, which allows many complicated systems to be treated on a first-principles level.
- Received 4 July 2016
- Revised 13 September 2016
DOI:https://doi.org/10.1103/PhysRevB.94.134303
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