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Title: Unravelling the mechanism of pressure induced polyamorphic transition in an inorganic molecular glass

Abstract

The atomic structure of a germanium doped phosphorous selenide glass of composition Ge2.8P57.7Se39.5 is determined as a function of pressure from ambient to 24 GPa using Monte-Carlo simulations constrained by high energy x-ray scattering data. The ambient pressure structure consists primarily of P4Se3 molecules and planar edge shared phosphorus rings, reminiscent of those found in red phosphorous as well as a small fraction of locally clustered corner-sharing GeSe4 tetrahedra. This low-density amorphous phase transforms into a high-density amorphous phase at ~6.3 GPa. The high-pressure phase is characterized by an extended network structure. The polyamorphic transformation between these two phases involves opening of the P3 ring at the base of the P4Se3 molecules and subsequent reaction with red phosphorus type moieties to produce a cross linked structure. The compression mechanism of the low-density phase involves increased molecular packing, whereas that of the high pressure phase involves an increase in the nearest-neighbor coordination number while the bond angle distributions broaden and shift to smaller angles. The entropy and volume changes associated with this polyamorphic transformation are positive and negative, respectively, and consequently the corresponding Clapeyron slope for this transition would be negative. This result has far reaching implications in our current understandingmore » of the thermodynamics of polyamorphic transitions in glasses and glass-forming liquids.« less

Authors:
 [1];  [2];  [3];  [4];  [5]
  1. Univ. of California, Santa Cruz, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Hacettepe Univ., Beytepe (Turkey)
  3. Corning Inc., Corning, NY (United States)
  4. Macquarie Univ., NSW (Australia)
  5. Univ. of California, Davis, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1695722
Grant/Contract Number:  
AC02-05CH11231; EAR 10–43050; DMR-1855176
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
42 ENGINEERING

Citation Formats

Kalkan, Bora, Okay, Gokce, Aitken, Bruce G., Clark, Simon M., and Sen, Sabyasachi. Unravelling the mechanism of pressure induced polyamorphic transition in an inorganic molecular glass. United States: N. p., 2020. Web. https://doi.org/10.1038/s41598-020-61997-x.
Kalkan, Bora, Okay, Gokce, Aitken, Bruce G., Clark, Simon M., & Sen, Sabyasachi. Unravelling the mechanism of pressure induced polyamorphic transition in an inorganic molecular glass. United States. https://doi.org/10.1038/s41598-020-61997-x
Kalkan, Bora, Okay, Gokce, Aitken, Bruce G., Clark, Simon M., and Sen, Sabyasachi. Mon . "Unravelling the mechanism of pressure induced polyamorphic transition in an inorganic molecular glass". United States. https://doi.org/10.1038/s41598-020-61997-x. https://www.osti.gov/servlets/purl/1695722.
@article{osti_1695722,
title = {Unravelling the mechanism of pressure induced polyamorphic transition in an inorganic molecular glass},
author = {Kalkan, Bora and Okay, Gokce and Aitken, Bruce G. and Clark, Simon M. and Sen, Sabyasachi},
abstractNote = {The atomic structure of a germanium doped phosphorous selenide glass of composition Ge2.8P57.7Se39.5 is determined as a function of pressure from ambient to 24 GPa using Monte-Carlo simulations constrained by high energy x-ray scattering data. The ambient pressure structure consists primarily of P4Se3 molecules and planar edge shared phosphorus rings, reminiscent of those found in red phosphorous as well as a small fraction of locally clustered corner-sharing GeSe4 tetrahedra. This low-density amorphous phase transforms into a high-density amorphous phase at ~6.3 GPa. The high-pressure phase is characterized by an extended network structure. The polyamorphic transformation between these two phases involves opening of the P3 ring at the base of the P4Se3 molecules and subsequent reaction with red phosphorus type moieties to produce a cross linked structure. The compression mechanism of the low-density phase involves increased molecular packing, whereas that of the high pressure phase involves an increase in the nearest-neighbor coordination number while the bond angle distributions broaden and shift to smaller angles. The entropy and volume changes associated with this polyamorphic transformation are positive and negative, respectively, and consequently the corresponding Clapeyron slope for this transition would be negative. This result has far reaching implications in our current understanding of the thermodynamics of polyamorphic transitions in glasses and glass-forming liquids.},
doi = {10.1038/s41598-020-61997-x},
journal = {Scientific Reports},
number = 1,
volume = 10,
place = {United States},
year = {2020},
month = {3}
}

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