Diffusion Quantum Monte Carlo Study of Martensitic Phase Transition: The Case of Phosphorene

Abstract

Recent technical advances in dealing with finite-size errors make quantum Monte Carlo methods quite appealing for treating extended systems in electronic structure calculations, especially when commonly-used density functional theory (DFT) methods might not be satisfactory. We present a theoretical study of martensitic phase transition of a two-dimensional phosphorene by employing diffusion Monte Carlo (DMC) approach to investigate the energetics of this phase transition. The DMC calculation supports DFT prediction of having a rather diffusive barrier that is characterized by having two transition states, in addition to confirming that the so-called black and blue phases of phosphorene are essentially degenerate. At the same time, the calculation shows the importance of treating correlation energy accurately for describing the energy changes in the martensitic phase transition, as is already widely appreciated for chemical bond formation/dissociation. Building on the atomistic characterization of the phase transition process, we also discuss how mechanical strain influences the stabilities of the two phases of phosphorene.