A first-principles investigation of the linear thermal expansion coefficients of BeF: giant thermal expansion.

We present the results of a theoretical investigation of the linear thermal expansion coefficients (TECs) of BeF, within a direct Grüneisen formalism where symmetry-preserving deformations are employed. The required physical quantities such as the optimized crystal structures, elastic constants, mode Grüneisen parameters, and phonon density of states are calculated from first-principles. BeF shows an extensive polymorphism at low pressures, and the lowest energy phases [α-cristobalite with space group (SG) 422 and its similar phase with SG 422] are considered in addition to the experimentally observed α-quartz phase. For benchmarking purposes, similar calculations are performed for the rutile phase of ZnF, where the volumetric TEC ( ), derived from the calculated linear TECs along the ( ) and ( ) directions, is in very good agreement with experimental data and previous theoretical results. For the considered phases of BeF, we do not find any negative thermal expansion (NTE). However we observe diverse thermal properties for the distinct phases. The linear TECs are very large, especially of the α-cristobalite phase and its similar phase, leading to giant (∼175 × 10 K at 300 K). The giant arises from large Grüneisen parameters of low-frequency phonon modes, and the elastic constant that is negatively signed and large in magnitude for the α-cristobalite phase. The elastic constants, high-frequency dielectric constants, Born effective charge tensors, and thermal properties of the above phases of BeF are reported for the first time and hence serve as predictions.