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Title: Polymorphism in elemental silicon: Probabilistic interpretation of the realizability of metastable structures

Abstract

With few systems of technological interest having been studied as extensively as elemental silicon, there currently exists a wide disparity between the number of predicted low-energy silicon polymorphs and those that have been experimentally realized as metastable at ambient conditions. We put forward an explanation for this disparity wherein the likelihood of formation of a given polymorph under near-equilibrium conditions can be estimated on the basis of mean-field isothermal-isobaric (N,p,T) ensemble statistics. The probability that a polymorph will be experimentally realized is shown to depend upon both the hypervolume of that structure's potential energy basin of attraction and a Boltzmann factor weight containing the polymorph's potential enthalpy per particle. Both attributes are calculated using density functional theory relaxations of randomly generated initial structures. We find that the metastable polymorphism displayed by silicon can be accounted for using this framework to the exclusion of a very large number of other low-energy structures.

Authors:
 [1];  [1]
  1. Colorado School of Mines, Golden, CO (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Next Generation of Materials by Design: Incorporating Metastability (CNGMD); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1416520
Alternate Identifier(s):
OSTI ID: 1408170
Report Number(s):
NREL/JA-5K00-70758
Journal ID: ISSN 2469-9950; PRBMDO
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 96; Journal Issue: 18; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; elemental silicon; polymorphism; metastable structures

Citation Formats

Jones, Eric B., and Stevanović, Vladan. Polymorphism in elemental silicon: Probabilistic interpretation of the realizability of metastable structures. United States: N. p., 2017. Web. doi:10.1103/PhysRevB.96.184101.
Jones, Eric B., & Stevanović, Vladan. Polymorphism in elemental silicon: Probabilistic interpretation of the realizability of metastable structures. United States. doi:10.1103/PhysRevB.96.184101.
Jones, Eric B., and Stevanović, Vladan. Fri . "Polymorphism in elemental silicon: Probabilistic interpretation of the realizability of metastable structures". United States. doi:10.1103/PhysRevB.96.184101. https://www.osti.gov/servlets/purl/1416520.
@article{osti_1416520,
title = {Polymorphism in elemental silicon: Probabilistic interpretation of the realizability of metastable structures},
author = {Jones, Eric B. and Stevanović, Vladan},
abstractNote = {With few systems of technological interest having been studied as extensively as elemental silicon, there currently exists a wide disparity between the number of predicted low-energy silicon polymorphs and those that have been experimentally realized as metastable at ambient conditions. We put forward an explanation for this disparity wherein the likelihood of formation of a given polymorph under near-equilibrium conditions can be estimated on the basis of mean-field isothermal-isobaric (N,p,T) ensemble statistics. The probability that a polymorph will be experimentally realized is shown to depend upon both the hypervolume of that structure's potential energy basin of attraction and a Boltzmann factor weight containing the polymorph's potential enthalpy per particle. Both attributes are calculated using density functional theory relaxations of randomly generated initial structures. We find that the metastable polymorphism displayed by silicon can be accounted for using this framework to the exclusion of a very large number of other low-energy structures.},
doi = {10.1103/PhysRevB.96.184101},
journal = {Physical Review B},
number = 18,
volume = 96,
place = {United States},
year = {2017},
month = {11}
}

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