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Title: Pressure Dependence of the Boson Peak of Glassy Glycerol

The pressure dependence of the Boson peak (BP) of glycerol, including its behavior across the liquid-glass transition, has been studied under pressure using Raman scattering. A significant increase of the BP frequency was observed with pressure up to 11 GPa at room temperature. The pressure dependence of BP frequency ν BP is proportional to (1+P/P 0) 1/3, where P and P 0 are the pressure and a constant, respectively, the spectra are consistent with a soft potential model. The characteristic length of medium range order is close in size to a cyclic trimer of glycerol molecules, which is predicted as the medium range order of a BP vibration using molecular dynamics simulations. The pressure dependence of a characteristic length of medium range order is nearly constant. The pressure induced structural changes in glycerol can be understood in terms of the shrinkage of voids with cyclic trimers remaining up to at least 11 GPa. Lastly, the pressure dependence of intermolecular O-H stretching mode indicates that the intermolecular hydrogen bond distance gradually decreases below the glass transition pressure of ~5 GPa, while it becomes nearly constant in the glassy state indicating the disappearance of the free volume in the dense glass.
Authors:
 [1] ;  [2] ; ORCiD logo [3] ;  [4]
  1. Carnegie Inst. of Washington, Washington, DC (United States). Geophysical Lab.
  2. George Mason Univ., Fairfax, VA (United States). College of Science
  3. George Washington Univ., Washington, DC (United States). Dept. of Civil and Environmental Engineering
  4. Univ. of Tsukuba (Japan). Division of Materials Science, Faculty of Pure and Applied Sciences
Publication Date:
Grant/Contract Number:
NA0002006; SC0001057
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 121; Journal Issue: 27; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Research Org:
Carnegie Inst. of Washington, Washington, DC (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1398767