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 »
- Authors:
-
- Univ. of California, Santa Cruz, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Hacettepe Univ., Beytepe (Turkey)
- Corning Inc., Corning, NY (United States)
- Macquarie Univ., NSW (Australia)
- Univ. of California, Davis, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (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. doi: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 = {Mon Mar 23 00:00:00 EDT 2020},
month = {Mon Mar 23 00:00:00 EDT 2020}
}
Works referenced in this record:
Fragile-to-strong transition in metallic glass-forming liquids
journal, July 2010
- Zhang, Chunzhi; Hu, Lina; Yue, Yuanzheng
- The Journal of Chemical Physics, Vol. 133, Issue 1
In situ high-pressure X-ray diffraction study of densification of a molecular chalcogenide glass
journal, September 2008
- Soyer Uzun, S.; Gaudio, S. J.; Sen, S.
- Journal of Physics and Chemistry of Solids, Vol. 69, Issue 9
Network vs Molecular Structural Characteristics of Ge-Doped Arsenic Sulfide Glasses: A Combined Neutron/X-ray Diffraction, Extended X-ray Absorption Fine Structure, and Raman Spectroscopic Study
journal, March 2009
- Soyer-Uzun, S.; Sen, S.; Aitken, B. G.
- The Journal of Physical Chemistry C, Vol. 113, Issue 15
Observation of a Pressure-Induced First-Order Polyamorphic Transition in a Chalcogenide Glass at Ambient Temperature
journal, July 2006
- Sen, S.; Gaudio, S.; Aitken, B. G.
- Physical Review Letters, Vol. 97, Issue 2
Polyamorphism and Pressure-Induced Metallization at the Rigidity Percolation Threshold in Densified GeSe 4 Glass
journal, March 2014
- Kalkan, Bora; Dias, Ranga P.; Yoo, Choong-Shik
- The Journal of Physical Chemistry C, Vol. 118, Issue 10
Partial structure factors from disordered materials diffraction data: An approach using empirical potential structure refinement
journal, September 2005
- Soper, A. K.
- Physical Review B, Vol. 72, Issue 10
Polyamorphism in water
journal, January 2010
- Mishima, Osamu
- Proceedings of the Japan Academy, Series B, Vol. 86, Issue 3
Viscosity Behavior Spanning Four Orders of Magnitude in As-S Melts under High Pressure
journal, March 2009
- Brazhkin, V. V.; Kanzaki, M.; Funakoshi, Ken-ichi
- Physical Review Letters, Vol. 102, Issue 11
31P solid-state NMR studies of the short-range order in phosphorus–selenium glasses
journal, January 2010
- Bytchkov, Aleksei; Fayon, Franck; Massiot, Dominique
- Physical Chemistry Chemical Physics, Vol. 12, Issue 7
Neutron studies of an inorganic plastic glass
journal, July 2011
- Wright, Adrian C.; Aitken, Bruce G.; Cuello, Gabriel
- Journal of Non-Crystalline Solids, Vol. 357, Issue 14
Melting studies of indium: determination of the structure and density of melts at high pressures and high temperatures
journal, October 2002
- Shen, Guoyin; Sata, Nagayoshi; Taberlet, Nicolas
- Journal of Physics: Condensed Matter, Vol. 14, Issue 44
Nature of the Polyamorphic Transition in Ice under Pressure
journal, January 2005
- Klotz, S.; Strässle, Th.; Nelmes, R. J.
- Physical Review Letters, Vol. 94, Issue 2
Hysteretically reversible phase transition in a molecular glass
journal, December 2012
- Kalkan, B.; Sonneville, C.; Martinet, C.
- The Journal of Chemical Physics, Vol. 137, Issue 22
A comparative study of the atomic structures of Ge-doped As4S3 and P4Se3 molecular glasses
journal, June 2019
- Kalkan, B.; Benmore, C. J.; Aitken, B. G.
- Journal of Non-Crystalline Solids, Vol. 514
Intermediate- and short-range order in phosphorus-selenium glasses
journal, April 2011
- Bytchkov, Aleksei; Miloshova, Mariana; Bychkov, Eugene
- Physical Review B, Vol. 83, Issue 14
Molecular Dynamics in Supercooled P−Se Liquids near the Glass Transition: Results from 31 P NMR Spectroscopy
journal, March 2011
- Gjersing, E. L.; Sen, S.; Aitken, B. G.
- The Journal of Physical Chemistry B, Vol. 115, Issue 12
Pressure-dependent structures of amorphous red phosphorus and the origin of the first sharp diffraction peaks
journal, October 2008
- Zaug, Joseph M.; Soper, Alan K.; Clark, Simon M.
- Nature Materials, Vol. 7, Issue 11
Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996
- Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
- High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
Supercooled and Glassy Water
journal, June 2003
- Debenedetti, Pablo G.; Stanley, H. Eugene
- Physics Today, Vol. 56, Issue 6
Topological versus chemical ordering in network glasses at intermediate and extended length scales
journal, May 2005
- Salmon, Philip S.; Martin, Richard A.; Mason, Philip E.
- Nature, Vol. 435, Issue 7038
Neutron studies of an inorganic plastic glass
journal, July 2011
- Wright, Adrian C.; Aitken, Bruce G.; Cuello, Gabriel
- Journal of Non-Crystalline Solids, Vol. 357, Issue 14
A comparative study of the atomic structures of Ge-doped As4S3 and P4Se3 molecular glasses
journal, June 2019
- Kalkan, B.; Benmore, C. J.; Aitken, B. G.
- Journal of Non-Crystalline Solids, Vol. 514
Molecular Dynamics in Supercooled P−Se Liquids near the Glass Transition: Results from 31 P NMR Spectroscopy
journal, March 2011
- Gjersing, E. L.; Sen, S.; Aitken, B. G.
- The Journal of Physical Chemistry B, Vol. 115, Issue 12
Polyamorphism and Pressure-Induced Metallization at the Rigidity Percolation Threshold in Densified GeSe 4 Glass
journal, March 2014
- Kalkan, Bora; Dias, Ranga P.; Yoo, Choong-Shik
- The Journal of Physical Chemistry C, Vol. 118, Issue 10
Network vs Molecular Structural Characteristics of Ge-Doped Arsenic Sulfide Glasses: A Combined Neutron/X-ray Diffraction, Extended X-ray Absorption Fine Structure, and Raman Spectroscopic Study
journal, March 2009
- Soyer-Uzun, S.; Sen, S.; Aitken, B. G.
- The Journal of Physical Chemistry C, Vol. 113, Issue 15
Topological versus chemical ordering in network glasses at intermediate and extended length scales
journal, May 2005
- Salmon, Philip S.; Martin, Richard A.; Mason, Philip E.
- Nature, Vol. 435, Issue 7038
Pressure-dependent structures of amorphous red phosphorus and the origin of the first sharp diffraction peaks
journal, October 2008
- Zaug, Joseph M.; Soper, Alan K.; Clark, Simon M.
- Nature Materials, Vol. 7, Issue 11
31P solid-state NMR studies of the short-range order in phosphorus–selenium glasses
journal, January 2010
- Bytchkov, Aleksei; Fayon, Franck; Massiot, Dominique
- Physical Chemistry Chemical Physics, Vol. 12, Issue 7
Supercooled and Glassy Water
journal, June 2003
- Debenedetti, Pablo G.; Stanley, H. Eugene
- Physics Today, Vol. 56, Issue 6
Hysteretically reversible phase transition in a molecular glass
journal, December 2012
- Kalkan, B.; Sonneville, C.; Martinet, C.
- The Journal of Chemical Physics, Vol. 137, Issue 22
Two-dimensional detector software: From real detector to idealised image or two-theta scan
journal, January 1996
- Hammersley, A. P.; Svensson, S. O.; Hanfland, M.
- High Pressure Research, Vol. 14, Issue 4-6, p. 235-248
Melting studies of indium: determination of the structure and density of melts at high pressures and high temperatures
journal, October 2002
- Shen, Guoyin; Sata, Nagayoshi; Taberlet, Nicolas
- Journal of Physics: Condensed Matter, Vol. 14, Issue 44
AsS Melt Under Pressure: One Substance, Three Liquids
journal, April 2008
- Brazhkin, V. V.; Katayama, Y.; Kondrin, M. V.
- Physical Review Letters, Vol. 100, Issue 14
Experimental Evidence for an Inorganic Molecular Glass
journal, August 1988
- Verrall, D. J.; Elliott, S. R.
- Physical Review Letters, Vol. 61, Issue 8
Comment on “Nature of the Polyamorphic Transition in Ice under Pressure”
journal, April 2006
- Tulk, C. A.; Benmore, C. J.; Klug, D. D.
- Physical Review Letters, Vol. 96, Issue 14
A beamline for high-pressure studies at the Advanced Light Source with a superconducting bending magnet as the source
journal, August 2005
- Kunz, Martin; MacDowell, Alastair A.; Caldwell, Wendel A.
- Journal of Synchrotron Radiation, Vol. 12, Issue 5
Polyamorphism in water
journal, January 2010
- Mishima, Osamu
- Proceedings of the Japan Academy, Series B, Vol. 86, Issue 3