Ab initio phase diagram of PbSe crystals calculated with the random phase approximation

Abstract

Understanding the phase behavior of semiconductor materials is important for applications in solid state physics and nanoscience. Accurate experimental data is often difficult to obtain due to strong kinetic effects. In this work, we calculate the temperature-pressure phase diagram of lead selenide (PbSe) using the random phase approximation (RPA), an accurate wavefunction based many-body technique. We consider three crystalline phases, the low pressure B1 phase (NaCltype), the intermediate B33 phase (CrB-type), and the high pressure B2 phase (CsCl-type). The electronic contributions to the free energy (at T = 0 K) are calculated in the Born-Oppenheimer approximation using the RPA, whereas phononic contributions are computed in the quasi-harmonic approximation using DFT and the PBEsol functional. At room temperature, we find transition pressures of 4.6±0.3 GPa for the B1 ↔ B33 transition and 18.7±0.3 GPa for the B33 ↔ B2 transition, in good agreement with experiments. In contrast to the interpretation of recent experiments, we observe a negative Clapeyron slope for both transitions. Gibbs free energy differences between competing structures have small gradients close to coexistence, consistent with pronounced hysteresis observed in experiments. The phase diagram presented in this work can serve as a reference for future studies of PbSe and should prove useful in the development of accurate and efficient force fields.

The Instability of Monolayer-Thick PbSe on VSe2

“…The calculations made use of the projector augmented wave (PAW) method as implemented in the Vienna ab initio simulation package (VASP), in conjunction with the generalized gradient-approximation exchange–correlation potential of Perdew–Burke–Ernzerhof (PBE) modified for solids: PBEsol . The choice of PBEsol was made based on previous works, which gave more accurate bulk properties of PbSe relative to PBE. , A planewave cutoff energy of 500 eV was employed. Wavefunctions were sampled using a Gamma-centered k-point grid of 8 × 8 × 1 (where the first two grid spacings are for directions in-plane and the last is normal to the surface) and a Gaussian smearing of 0.1 eV.…”

“…48 The choice of PBEsol was made based on previous works, which gave more accurate bulk properties of PbSe relative to PBE. 49,50 A planewave cutoff energy of 500 eV was employed. Wavefunctions were sampled using a Gamma-centered k-point grid of 8 × 8 × 1 (where the first two grid spacings are for directions in-plane and the last is normal to the surface) and a Gaussian smearing of 0.1 eV.…”