The extended stability range of phosphorus allotropes

Area of Science:

• Solid-state chemistry
• Materials science
• Computational chemistry

Background:

• Phosphorus exhibits remarkable structural diversity, with ongoing research into new crystalline allotropes.
• Understanding the stability and properties of these allotropes is crucial for materials science applications.

Purpose of the Study:

• To comprehensively map the stability range of known and novel crystalline phosphorus allotropes.
• To predict the structures of unexplored phosphorus nanorods, such as [P12] and [P14].
• To evaluate the accuracy of different computational methods in describing phosphorus allotropes.

Main Methods:

• Utilized ab initio calculations to investigate the structural and stability properties of phosphorus allotropes.
• Employed Density Functional Theory (DFT) functionals, including GGA, LDA, and GGA-D2.
• Compared computational predictions with experimental data for established phosphorus forms.

Main Results:

• Presented a complete stability range for various crystalline phosphorus allotropes, including tubular forms.
• Successfully predicted the crystal structures of [P12] and [P14] nanorods.
• Demonstrated that the GGA-D2 approach provides excellent agreement with experimental data for phosphorus allotropes, outperforming GGA and LDA.

Conclusions:

• The GGA-D2 method is highly reliable for predicting solid structures of phosphorus nanorods and other allotropes.
• This work provides a foundational understanding of phosphorus allotrope stability, guiding future experimental and theoretical research.