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Phosphorus allotropes: Stability of black versus red phosphorus re-examined by means of the van der Waals inclusive density functional method

Journal Article · · Physical Review B
 [1];  [1];  [1]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
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We evaluate the energetic stabilities of white, red, and black allotropes of phosphorus using density functional theory (DFT) and hybrid functional methods, van der Waals (vdW) corrections (DFT+vdW and hybrid+vdW), vdW density functionals, and random phase approximation (RPA). In this work, we find that stability of black phosphorus over red-V (i.e., the violet form) is not ubiquitous among these methods, and the calculated enthalpies for the reaction phosphorus (red-V)→ phosphorus (black) are scattered between –20 and 40 meV/atom. With local density and generalized gradient approximations, and hybrid functionals, mean absolute errors (MAEs) in densities of P allotropes relative to experiments are found to be around 10%–25%, whereas with vdW-inclusive methods, MAEs in densities drop below ~5%. While the inconsistency among the density functional methods could not shed light on the stability puzzle of black versus red phosphorus, comparison of their accuracy in predicting densities and the supplementary RPA results on relative stabilities indicate that opposite to the common belief, black and red phosphorus are almost degenerate, or the red-V (violet) form of phosphorus might even be the ground state.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
The Dow Chemical Company; USDOE; USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231; FG02-07ER46433
OSTI ID:
1544385
Alternate ID(s):
OSTI ID: 1367364
Journal Information:
Physical Review B, Journal Name: Physical Review B Journal Issue: 21 Vol. 95; ISSN 2469-9950; ISSN PRBMDO
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (7)

Structure and Properties of Violet Phosphorus and Its Phosphorene Exfoliation journal December 2019
Structure and Properties of Violet Phosphorus and Its Phosphorene Exfoliation journal December 2019
Embracing high performance potassium-ion batteries with phosphorus-based electrodes: a review journal January 2019
Strain-induced effects in zigzag-edged blue phosphorene nanoribbons with edge sulfur passivation journal September 2018
Phase stability and interlayer interaction of blue phosphorene journal August 2018
Performance of the strongly constrained and appropriately normed density functional for solid-state materials journal June 2018
Electronic Structural and Optical Properties of Multilayer Blue Phosphorus: A First-Principle Study journal January 2019

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