Development of a Transferable Reactive Force Field of P/H Systems: Application to the Chemical and Mechanical Properties of Phosphorene

TL;DR

This paper develops a transferable reactive force field for phosphorus/hydrogen systems using ReaxFF, enabling accurate large-scale simulations of phosphorene's chemical and mechanical properties, including defect effects and heterostructures.

Contribution

The authors created a new ReaxFF parameter set for P/H systems with improved accuracy and transferability, extending its application to various phosphorus-based materials and defects.

Findings

ReaxFF accurately models pristine and defected black phosphorene.

Single vacancies weaken phosphorene more than double vacancies.

Mechanical response varies with defect type and direction.

Abstract

ReaxFF provides a method to model reactive chemical systems in large-scale molecular dynamics simulations. Here, we developed ReaxFF parameters for phosphorus and hydrogen to give a good description of the chemical and mechanical properties of pristine and defected black phosphorene. ReaxFF for P/H is transferable to a wide range of phosphorus and hydrogen containing systems including bulk black phosphorus, blue phosphorene, edge-hydrogenated phosphorene, phosphorus clusters and phosphorus hydride molecules. The potential parameters were obtained by conducting unbiased global optimization with respect to a set of reference data generated by extensive ab initio calculations. We extend ReaxFF by adding a 60{\deg} correction term which significantly improves the description of phosphorus clusters. Emphasis has been put on obtaining a good description of mechanical response of black phosphorene with different types of defects. Compared to nonreactive SW potential [1], ReaxFF for P/H systems provides a huge improvement in describing the mechanical properties the pristine and defected black phosphorene and the thermal stability of phosphorene nanotubes. A counterintuitive phenomenon is observed that single vacancies weaken the black phosphorene more than double vacancies with higher formation energy. Our results also show that mechanical response of black phosphorene is more sensitive to defects for the zigzag direction than for the armchair direction. Since ReaxFF allows straightforward extensions to the heterogeneous systems, such as oxides, nitrides, ReaxFF parameters for P/H systems build a solid foundation for the reactive force field description of heterogeneous P systems, including P-containing 2D van der Waals heterostructures, oxides, etc.